Organic Materials with Special Optical Effects

Abstract

The present invention relates to a compound of the following formula (I). The invention also relates to uses thereof as a chromophore as such or for building pigments displaying special optical effects, including metal-like reflection.

##STR00001##

Claims

1. A compound of following general formula (I): ##STR00084## wherein: R.sub.0 represents a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.5, SR.sub.6, NR.sub.7R.sub.8, PR.sub.9R.sub.10, COR.sub.11, CO.sub.2R.sub.12, CONR.sub.13R.sub.14, SO.sub.2R.sub.15, SO.sub.3H, CN, NO.sub.2, OCOR.sub.16, OCO.sub.2R.sub.17, NR.sub.18COR.sub.19 or NR.sub.20SO.sub.2R.sub.21 group, or is selected from the group consisting of: ##STR00085## wherein: Z represents C or N.sup.+ A.sub.z.sup. and Z represents N or N.sup.+R.sub.c A.sub.z.sup., wherein A.sub.z.sup. represents a monovalent organic or inorganic anion, and R.sub.c represents a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, R.sub.a and R.sub.e each represent, independently of each other, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.22 or SR.sub.23 group, and R.sub.b, R.sub.c and R.sub.d each represent, independently of each other, a hydrogen atom, a halogen atom or a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group; R.sub.1R.sub.1, and R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; R.sub.4R.sub.4, and R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; with the proviso that when R.sub.1 and R.sub.4 are the same, at least one of R.sub.a and R.sub.e is not the same as R.sub.1; or R.sub.4 and R.sub.4 form together a bond or a chain selected from the group consisting of C(R.sub.74R.sub.75), (CH.sub.2).sub.n, Si(R.sub.76R.sub.77), (CH.sub.2).sub.pY(CH.sub.2).sub.q, and Y(CR.sub.78R.sub.79).sub.rY, wherein: Y and Y each represent, independently of each other, O, S or NR.sub.80, n is equal to 2 or 3, p is equal to 1 or 2, q is equal to 0 or 1, r is equal to 1 or 2, R.sub.74, R.sub.75, R.sub.78 to R.sub.80 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or an aryl group, and R.sub.76 and R.sub.77 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl or an aryl group; R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.42, SR.sub.43, NR.sub.44R.sub.45, COR.sub.46, CO.sub.2R.sub.47 or CONR.sub.48R.sub.49 group; L.sub.X=L.sub.X, and L.sub.X represents a bond, or a group selected from the group consisting of: ##STR00086## XX, and X represents NR.sub.50R.sub.51, heterocycle, heteroaryl or aryl, wherein: said heterocycle and heteroaryl group comprise at least one nitrogen atom bearing a lone pair of electrons conjugated with C.sup.+, and are optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.56, SR.sub.57 and NR.sub.58R.sub.59 group, and said aryl is para-substituted by a NR.sub.60R.sub.61 group, and optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.66, SR.sub.67 and NR.sub.68R.sub.69 group; or R.sub.1 together with R.sub.2, and R.sub.1 together with R.sub.2 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or R.sub.3 together with R.sub.4, and R.sub.3 together with R.sub.4 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54 or SR.sub.55; and R.sub.2 and NR.sub.50, and R.sub.2 and NR.sub.50; R.sub.2 and PR.sub.52, and R.sub.2 and PR.sub.52; R.sub.2 and OR.sub.54, and R.sub.2 and OR.sub.54; or R.sub.2 and SR.sub.55, and R.sub.2 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and/or R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51; R.sub.3 and PR.sub.53, and R.sub.3 and PR.sub.53; R.sub.3 and OR.sub.54, and R.sub.3 and OR.sub.54; or R.sub.3 and SR.sub.55, and R.sub.3 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and R.sub.50, R.sub.51, R.sub.52 and R.sub.53 represent respectively R.sub.50, R.sub.51, R.sub.52 and R.sub.53 when they are not linked with R.sub.2 or R.sub.3; and R.sub.5 to R.sub.53, R.sub.56 to R.sub.63, R.sub.66 to R.sub.73 and R.sub.81 to R.sub.84 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and R.sub.54, R.sub.55, R.sub.64 and R.sub.65 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and A.sup. represents a monovalent or multivalent, organic or inorganic anion.

2. The compound according to claim 1, wherein: R.sub.0 is as defined in claim 1; R.sub.1R.sub.1, and R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.3OR.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; R.sub.4R.sub.4, and R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; with the proviso that when R.sub.1 and R.sub.4 are the same, at least one of R.sub.a and R.sub.e is not the same as R.sub.1; R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.42, SR.sub.43, NR.sub.44R.sub.45, COR.sub.46, CO.sub.2R.sub.47 or CONR.sub.48R.sub.49 group; L.sub.X=L.sub.X, and L.sub.X represents a bond, or a group selected from the group consisting of: ##STR00087## XX, and X represents NR.sub.50R.sub.51, heterocycle, heteroaryl or aryl, wherein: said heterocycle and heteroaryl group comprise at least one nitrogen atom bearing a lone pair of electrons conjugated with C.sup.+, and are optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.56, SR.sub.57 and NR.sub.58R.sub.59 group, and said aryl is para-substituted by a NR.sub.60R.sub.61 group, and optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.66, SR.sub.67 and NR.sub.68R.sub.69 group; or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54 or SR.sub.55; and R.sub.2 and NR.sub.50, and R.sub.2 and NR.sub.50; R.sub.2 and PR.sub.52, and R.sub.2 and PR.sub.52; R.sub.2 and OR.sub.54, and R.sub.2 and OR.sub.54; or R.sub.2 and SR.sub.55, and R.sub.2 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and/or R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51; R.sub.3 and PR.sub.53, and R.sub.3 and PR.sub.53; R.sub.3 and OR.sub.54, and R.sub.3 and OR.sub.54; or R.sub.3 and SR.sub.55, and R.sub.3 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and R.sub.50, R.sub.51, R.sub.52 and R.sub.53 represent respectively R.sub.50, R.sub.51, R.sub.52 and R.sub.53 when they are not linked with R.sub.2 or R.sub.3; and R.sub.5 to R.sub.88 are as defined in claim 1; and A.sup. represents a monovalent or multivalent, organic or inorganic anion.

3. The compound according to claim 1, wherein R.sub.0 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, NR.sub.7R.sub.8, CN, CF.sub.3 or NO.sub.2 group, or is selected from the group consisting of: ##STR00088## wherein: R.sub.a, and R.sub.e each represent, independently of each other, a methyl, OCH.sub.3 or phenyl group, and R.sub.b, R.sub.c and R.sub.d each represent a hydrogen atom.

4. The compound according to claim 1, wherein R.sub.1R.sub.4 and R.sub.1 represents a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, CH.sub.2OR.sub.24, CH.sub.2SR.sub.25, OR.sub.26 or SR.sub.27 group.

5. The compound according to claim 1, wherein L.sub.X represents a bond.

6. The compound according to claim 1, wherein: R.sub.2R.sub.3 and R.sub.2 represents a hydrogen atom, or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51; and R.sub.2 and NR.sub.50, R.sub.2 and NR.sub.50, R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51 form together with the carbon atoms that carry them a heterocycle group.

7. The compound according to claim 1, wherein it is selected from the group consisting of: ##STR00089## ##STR00090## ##STR00091##

8. The compound according to claim 1, wherein A.sup. represents a hexafluorophosphate, tetrafluoroborate, tetraphenylborate, 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (DDQH.sup.), halide or triflate anion.

9. A supramolecular material, comprising a self-assembly of a compound of following general formula (I): ##STR00092## wherein: R.sub.0 represents a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.5, SR.sub.6, NR.sub.7R.sub.8, PR.sub.9R.sub.10, COR.sub.11, CO.sub.2R.sub.12, CONR.sub.13R.sub.14, SO.sub.2R.sub.15, SO.sub.3H, CN, NO.sub.2, OCOR.sub.16, OCO.sub.2R.sub.17, NR.sub.18COR.sub.19 or NR.sub.20SO.sub.2R.sub.21 group, or is selected from the group consisting of: ##STR00093## wherein: Z represents C or N.sup.+ A.sub.z.sup. and Z represents N or N.sup.+R.sub.c A.sub.z.sup., wherein A.sub.z.sup. represents a monovalent organic or inorganic anion, and R.sub.c represents a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, R.sub.a and R.sub.e each represent, independently of each other, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.22 or SR.sub.23 group, and R.sub.b, R.sub.c and R.sub.d each represent, independently of each other, a hydrogen atom, a halogen atom or a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group; R.sub.1R.sub.1, and R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; R.sub.4R.sub.4, and R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; with the proviso that when R.sub.1 and R.sub.4 are the same, at least one of R.sub.a and R.sub.e is not the same as R.sub.1; or R.sub.4 and R.sub.4 form together a bond or a chain selected from the group consisting of C(R.sub.74R.sub.75), (CH.sub.2).sub.n, Si(R.sub.76R.sub.77), (CH.sub.2).sub.pY(CH.sub.2).sub.q, and Y(CR.sub.78R.sub.79).sub.rY, wherein: Y and Y each represent, independently of each other, O, S or NR.sub.80, n is equal to 2 or 3, p is equal to 1 or 2, q is equal to 0 or 1, r is equal to 1 or 2, R.sub.74, R.sub.75, R.sub.78 to R.sub.80 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or an aryl group, and R.sub.76 and R.sub.77 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl or an aryl group; R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.42, SR.sub.43, NR.sub.44R.sub.45, COR.sub.46, CO.sub.2R.sub.47 or CONR.sub.48R.sub.49 group; L.sub.X=L.sub.X, and L.sub.X represents a bond, or a group selected from the group consisting of: ##STR00094## wherein R.sub.f, R.sub.g and R.sub.h each represent, independently of each other, a hydrogen or halogen atom, a (C.sub.1-C.sub.6)alkyl or (C.sub.1-C.sub.6)haloalkyl group; XX, and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54, SR.sub.55, heterocycle, heteroaryl or aryl, wherein: said heterocycle and heteroaryl group comprise at least one heteroatom bearing a lone pair of electrons conjugated with C.sup.+, and are optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.56, SR.sub.57 and NR.sub.58R.sub.59, and said aryl is para-substituted by a group selected from NR.sub.60R.sub.61, PR.sub.62R.sub.63, OR.sub.64 and SR.sub.65, and optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.66, SR.sub.67 and NR.sub.68R.sub.69; or R.sub.1 together with R.sub.2, and R.sub.1 together with R.sub.2 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or R.sub.3 together with R.sub.4, and R.sub.3 together with R.sub.4 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54 or SR.sub.55; and R.sub.2 and NR.sub.50, and R.sub.2 and NR.sub.50; R.sub.2 and PR.sub.2, and R.sub.2 and PR.sub.2; R.sub.2 and OR.sub.54, and R.sub.2 and OR.sub.54; or R.sub.2 and SR.sub.55, and R.sub.2 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and/or R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51; R.sub.3 and PR.sub.53, and R.sub.3 and PR.sub.53; R.sub.3 and OR.sub.54, and R.sub.3 and OR.sub.54; or R.sub.3 and SR.sub.55, and R.sub.3 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and R.sub.50, R.sub.51, R.sub.52 and R.sub.53 represent respectively R.sub.50, R.sub.51, R.sub.52 and R.sub.53 when they are not linked with R.sub.2 or R.sub.3; and/or L.sub.X=L.sub.X and L.sub.x represents ##STR00095## and R.sub.2 and R.sub.f, and R.sub.2 and R.sub.f; or R.sub.2 and R.sub.g and R.sub.2 and R.sub.g form together with the carbon atoms that carry them a cycloalkenyl or aryl group; and/or R.sub.3 and R.sub.g, and R.sub.3 and R.sub.g form together with the carbon atoms that carry them a cycloalkenyl or aryl group; and R.sub.f, R.sub.g and R.sub.h represent respectively R.sub.f, R.sub.g and R.sub.h when they are not linked with R.sub.2 or R.sub.3; and R.sub.5 to R.sub.53, R.sub.56 to R.sub.63, R.sub.66 to R.sub.73 and R.sub.81 to R.sub.84 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and R.sub.54, R.sub.55, R.sub.64 and R.sub.65 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and A.sup. represents a monovalent or multivalent, organic or inorganic anion.

10. The supramolecular material according to claim 9, wherein: R.sub.0 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, NR.sub.7R.sub.8, CN, CF.sub.3 or NO.sub.2 group, or is selected from the group consisting of: ##STR00096## wherein: R.sub.a, and R.sub.e each represent, independently of each other, a methyl, OCH.sub.3 or phenyl group, and R.sub.b, R.sub.c and R.sub.d each represent a hydrogen atom; R.sub.1R.sub.4 and R.sub.1 represents a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, CH.sub.2OR.sub.24, CH.sub.2SR.sub.25, OR.sub.26 or SR.sub.27 group; L.sub.X=L.sub.X and L.sub.x represents a bond; and R.sub.2R.sub.3 and R.sub.2 represents a hydrogen atom.

11. The supramolecular material according to claim 9, wherein said compound is selected from the group consisting of: ##STR00097## ##STR00098## ##STR00099##

12. The supramolecular material according to claim 9, wherein said compound is a compound of formula (I) wherein: L.sub.X=L.sub.X, and L.sub.X represents a bond, or a group selected from the group consisting of: ##STR00100## and XX, and X represents NR.sub.50R.sub.51, heterocycle, heteroaryl or aryl, wherein: said heterocycle and heteroaryl group comprise at least one nitrogen atom bearing a lone pair of electrons conjugated with C.sup.+, and are optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.56, SR.sub.57 and NR.sub.58R.sub.59 group, and said aryl is para-substituted by a NR.sub.60R.sub.61 group, and optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.66, SR.sub.67 and NR.sub.68R.sub.69 group; or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54 or SR.sub.55; and R.sub.2 and NR.sub.50, and R.sub.2 and NR.sub.50; R.sub.2 and PR.sub.52, and R.sub.2 and PR.sub.52; R.sub.2 and OR.sub.54, and R.sub.2 and OR.sub.54; or R.sub.2 and SR.sub.55, and R.sub.2 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.1, SR.sub.82 and NR.sub.83R.sub.84; and/or R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51; R.sub.3 and PR.sub.53, and R.sub.3 and PR.sub.53; R.sub.3 and OR.sub.54, and R.sub.3 and OR.sub.54; or R.sub.3 and SR.sub.55, and R.sub.3 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and R.sub.50, R.sub.51, R.sub.52 and R.sub.53 represent respectively R.sub.50, R.sub.51, R.sub.52 and R.sub.53 when they are not linked with R.sub.2 or R.sub.3.

13. The supramolecular material according to claim 9, wherein A.sup. represents a hexafluorophosphate, tetrafluoroborate, tetraphenylborate, DDQH.sup., halide or triflate anion.

14. The supramolecular material according to claim 9, wherein said supramolecular material is a pigment.

15. (canceled)

16. The supramolecular material according to claim 9, wherein said supramolecular material is a metal-like reflective coating.

17. The compound according to claim 1, wherein R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent a hydrogen atom.

18. The compound according to claim 1, wherein wherein R.sub.0 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or NO.sub.2 group.

19. The supramolecular material according to claim 9, wherein R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent a hydrogen atom.

20. The supramolecular material according to claim 9, wherein wherein R.sub.0 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or NO.sub.2 group.

21. A reflective or photonic or nanophotonic or optoelectronic device, comprising at least one compound of following general formula (I): ##STR00101## wherein: R.sub.0 represents a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.5, SR.sub.6, NR.sub.7R.sub.8, PR.sub.9R.sub.10, COR.sub.11, CO.sub.2R.sub.12, CONR.sub.13R.sub.14, SO.sub.2R.sub.15, SO.sub.3H, CN, NO.sub.2, OCOR.sub.16, OCO.sub.2R.sub.17, NR.sub.18COR.sub.19 or NR.sub.20SO.sub.2R.sub.21 group, or is selected from the group consisting of: ##STR00102## wherein: Z represents C or N.sup.+ A.sub.z.sup. and Z represents N or N.sup.+R.sub.c A.sub.z.sup., wherein A.sub.z.sup. represents a monovalent organic or inorganic anion, and R.sub.c represents a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, R.sub.a and R.sub.e each represent, independently of each other, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.22 or SR.sub.23 group, and R.sub.b, R.sub.c and R.sub.d each represent, independently of each other, a hydrogen atom, a halogen atom or a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group; R.sub.1R.sub.1, and R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; R.sub.4R.sub.4, and R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, PR.sub.30R.sub.31, COR.sub.32, CO.sub.2R.sub.33, CONR.sub.34R.sub.35, OCOR.sub.36, OCO.sub.2R.sub.37, NR.sub.38COR.sub.39, or NR.sub.40SO.sub.2R.sub.41 group, wherein m and m are, independently of each other, equal to 1, 2 or 3; with the proviso that when R.sub.1 and R.sub.4 are the same, at least one of R.sub.a and R.sub.e is not the same as R.sub.1; or R.sub.4 and R.sub.4 form together a bond or a chain selected from the group consisting of C(R.sub.74R.sub.75), (CH.sub.2).sub.n, Si(R.sub.76R.sub.77), (CH.sub.2).sub.pY(CH.sub.2).sub.q, and Y(CR.sub.78R.sub.79).sub.rY, wherein: Y and Y each represent, independently of each other, O, S or NR.sub.80, n is equal to 2 or 3, p is equal to 1 or 2, q is equal to 0 or 1, r is equal to 1 or 2, R.sub.74, R.sub.75, R.sub.78 to R.sub.80 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or an aryl group, and R.sub.76 and R.sub.77 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl or an aryl group; R.sub.2R.sub.2, R.sub.3R.sub.3, and R.sub.2 and R.sub.3 each represent, independently of each other, a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle, heterocycle-(C.sub.1-C.sub.6)alkyl, OR.sub.42, SR.sub.43, NR.sub.44R.sub.45, COR.sub.46, CO.sub.2R.sub.47 or CONR.sub.48R.sub.49 group; L.sub.X=L.sub.X, and L.sub.X represents a bond, or a group selected from the group consisting of: ##STR00103## wherein R.sub.f, R.sub.g and R.sub.h each represent, independently of each other, a hydrogen or halogen atom, a (C.sub.1-C.sub.6)alkyl or (C.sub.1-C.sub.6)haloalkyl group; XX, and X represents NR.sub.50R.sub.51, PR.sub.52R.sub.53, OR.sub.54, SR.sub.55, heterocycle, heteroaryl or aryl, wherein: said heterocycle and heteroaryl group comprise at least one heteroatom bearing a lone pair of electrons conjugated with C.sup.+, and are optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.56, SR.sub.57 and NR.sub.58R.sub.59, and said aryl is para-substituted by a group selected from NR.sub.60R.sub.61, PR.sub.62R.sub.63, OR.sub.64 and SR.sub.65, and optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.66, SR.sub.67 and NR.sub.68R.sub.69; or R.sub.1 together with R.sub.2, and R.sub.1 together with R.sub.2 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or R.sub.3 together with R.sub.4, and R.sub.3 together with R.sub.4 form together with the carbon atoms that carry them an identical cycle selected from the group consisting of cycloalkenyl, heterocycle, aryl and heteroaryl, said cycle being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.70, SR.sub.71 and NR.sub.72R.sub.73; and/or L.sub.X=L.sub.X and L.sub.X represents a bond; XX and X represents NR.sub.50R.sub.51, PR.sub.2R.sub.53, OR.sub.54 or SR.sub.55; and R.sub.2 and NR.sub.50, and R.sub.2 and NR.sub.50; R.sub.2 and PR.sub.52, and R.sub.2 and PR.sub.2; R.sub.2 and OR.sub.54, and R.sub.2 and OR.sub.54; or R.sub.2 and SR.sub.55, and R.sub.2 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and/or R.sub.3 and NR.sub.51, and R.sub.3 and NR.sub.51; R.sub.3 and PR.sub.53, and R.sub.3 and PR.sub.53; R.sub.3 and OR.sub.54, and R.sub.3 and OR.sub.54; or R.sub.3 and SR.sub.55, and R.sub.3 and SR.sub.55 form together with the carbon atoms that carry them a heterocycle or heteroaryl group, said group being optionally substituted by one or more groups selected from a halogen atom, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.81, SR.sub.82 and NR.sub.83R.sub.84; and R.sub.50, R.sub.51, R.sub.52 and R.sub.53 represent respectively R.sub.50, R.sub.51, R.sub.52 and R.sub.53 when they are not linked with R.sub.2 or R.sub.3; and/or L.sub.X=L.sub.X and L.sub.x represents ##STR00104## and R.sub.2 and R.sub.f, and R.sub.2 and R.sub.f; or R.sub.2 and R.sub.g and R.sub.2 and R.sub.g form together with the carbon atoms that carry them a cycloalkenyl or aryl group; and/or R.sub.3 and R.sub.g, and R.sub.3 and R.sub.g form together with the carbon atoms that carry them a cycloalkenyl or aryl group; and R.sub.f, R.sub.g and R.sub.h represent respectively R.sub.f, R.sub.g and R.sub.h when they are not linked with R.sub.2 or R.sub.3; and R.sub.5 to R.sub.53, R.sub.56 to R.sub.63, R.sub.66 to R.sub.73 and R.sub.81 to R.sub.84 each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and R.sub.54, R.sub.55, R.sub.64 and R.sub.65 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle or heterocycle-(C.sub.1-C.sub.6)alkyl group, said group being optionally substituted by one or more groups selected from a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, OR.sub.85, SR.sub.86 and NR.sub.87R.sub.88 group, wherein R.sub.85 to R.sub.88 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and A.sup. represents a monovalent or multivalent, organic or inorganic anion.

Description

FIGURES

[0387] FIG. 1 represents the absorption spectra of compounds 1-PF.sub.6.sup. and 2-PF.sub.6.sup. in solution in acetonitrile.

[0388] FIG. 2 corresponds to a picture of a 10.sup.5 mol.Math.L.sup.1 solution of compound 1-PF.sub.6.sup. in acetonitrile, characterized by its intense deep blue color.

[0389] FIG. 3 corresponds to a picture of a gold-like mirror of compound 1-PF.sub.6.sup. that forms on the wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 1-PF.sub.6.sup..

[0390] FIG. 4a represents a macroscopic view of compound 1-PF.sub.6.sup. in its microcrystallized form, characterized by its metallic and gold flakes appearance.

[0391] FIGS. 4b and 4c both display microscopic views of compound 1-PF.sub.6.sup. in the form of large single crystals, obtained with a Zeiss-Stemi 2000-C microscope.

[0392] FIG. 5 displays a microscopic view of iridescent compound 2-PF.sub.6.sup. in a polycrystalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0393] FIG. 6 represents the absorption spectra of compounds 27-PF.sub.6.sup., 28-PF.sub.6.sup., 29-PF.sub.6.sup., 30-PF.sub.6.sup., 32-PF.sub.6.sup. in solution in acetonitrile.

[0394] FIGS. 7a and 7b both display microscopic views of compound 27-DDQH.sup. in a polycrystalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0395] FIGS. 8a and 8b both display microscopic views of compound 27-PF.sub.6.sup. in a polycrystalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0396] FIGS. 9a and 9b both display microscopic views of compound 28-PF.sub.6.sup. in the form of large single (columnar) crystals, obtained with a Zeiss-Stemi 2000-C microscope.

[0397] FIGS. 10a and 10b both display microscopic views of compound 29-DDQH.sup. in its microcrystallized form, characterized by its metallic and gold flakes appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0398] FIGS. 11a and 11b both display microscopic views of compound 29-PF.sub.6.sup. in the form of large single crystals, obtained with a Zeiss-Stemi 2000-C microscope.

[0399] FIGS. 12a and 12b both display microscopic views of compound 30-PF.sub.6.sup. in a polycrystalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0400] FIGS. 13a and 13b both display microscopic views of compound 32-DDQH.sup. in its microcrystallized form, characterized by its metallic and gold flakes appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0401] FIGS. 14a and 14b both display microscopic views of compound 32-PF.sub.6.sup. in a polycrystalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0402] The examples that follow illustrate the invention without limiting its scope in any way.

EXAMPLES

[0403] The following abbreviations have been used: [0404] Ac: Acetyl (COCH.sub.3) [0405] Bn: Benzyl (CH.sub.2Ph) [0406] Bu: Butyl (CH.sub.2CH.sub.2CH.sub.2CH.sub.3) [0407] ca.: circa [0408] DDQ: 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone [0409] DMF: Dimethylformamide [0410] EDG: Electron-Donating Group [0411] equiv.: equivalent [0412] ESI: Electrospray ionisation [0413] Et: Ethyl (CH.sub.2CH.sub.3) [0414] Me: Methyl (CH.sub.3) [0415] MS: Mass Spectroscopy [0416] NBS: N-Bromosuccinimide [0417] NIR: Near Infra Red [0418] NMR: Nuclear Magnetic Resonance [0419] Ph: Phenyl (C.sub.6H.sub.5) [0420] THF: Tetrahydrofuran [0421] TMEDA: Tetramethylethylenediamine [0422] TMSI: Trimethylsilyl iodide [0423] vis: visible [0424] wt: weight

ISynthesis of the Compounds According to the Invention

I-1. General Procedures

General Procedure A

[0425] Compounds of the formula A (para-electrodonating ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 1, wherein X is an EDG:

##STR00037##

[0426] A meta-disubstituted electrodonating precursor (either commercially available or not) is engaged in a lithiation reaction. Depending on the nature of the starting material, a prior step of para bromination may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with ethyl formate yielding a carbinol intermediate [Patents], itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Abis

[0427] Compounds of the formula A (para-electrodonating ortho-substituted diphenylcarbenium) can also be prepared by the following Reaction Scheme 2 as a one pot reaction (Scheme 2 a)) or as a two-step reaction (Scheme 2b)), wherein X is an EDG:

##STR00038##

[0428] A meta-disubstituted electrodonating precursor (either commercially available or not) is engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002]. The resulting methylene, that often easily crystallizes is then oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure B

[0429] Compounds of the formula B (para-diamino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 3:

##STR00039##

[0430] A meta-disubstituted diallylamino precursor (itself synthesized from its corresponding parent aniline, either commercially available or not, according to a classical procedure [Egawa2011]) is engaged in a lithiation reaction. Depending on the nature of the starting material, a step of para bromination prior nitrogen allylation may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with diethyl carbonate yielding a congested bis(diallylamino) benzophenone precursor, which amine groups can be deprotected in presence of palladium tetrakis and 1,3-dimethylbarbituric acid [Egawa2011]. The ketone function can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure C

[0431] Compounds of the formula C (julolidine-type ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 4:

##STR00040##

[0432] A disubstituted julolidine-type precursor (itself synthesized from its corresponding parent aniline, either commercially available or not, according to a classical procedure [Dance2008]) is engaged in a lithiation reaction. Depending on the nature of the starting material, a prior step of para bromination may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with ethyl formate yielding a carbinol intermediate [Patents], itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Cbis

[0433] Compounds of the formula C (julolidine-type ortho-substituted diphenylcarbenium) can also be prepared by the following Reaction Scheme 5 as a one pot reaction (Scheme 5 a)) or as a two-step reaction (Scheme 5 b)):

##STR00041##

[0434] A disubstituted julolidine-type precursor (itself synthesized from its corresponding parent aniline, either commercially available or not, according to a classical procedure [Dance2008]) is engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002]. The resulting methylene, that often easily crystallizes is then oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure D

[0435] Compounds of the formula D can be obtained from the key benzophenone (KB) precursor prepared by the following Reaction Scheme 6:

##STR00042##

[0436] A meta-disubstituted anisole (either commercially available or not) is para-brominated according to a classical procedure employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The resulting bromoanisole is then engaged in a lithiation reaction, and the intermediate is quenched with ethyl formate yielding a carbinol intermediate [Patents] which is subsequently oxidized to the corresponding ketone by using DDQ [Torricelli2013]. The methoxy groups of this benzophenone are demethylated by using BBr.sub.3 and the resulting phenol moieties are then reacted with triflic anhydride to give the desired key benzophenone derivative, KB.

[0437] Compounds of the formula D (aryl extended ortho-substituted diphenylcarbenium) can then be prepared by the following Reaction Scheme 7, wherein X is an EDG:

##STR00043##

[0438] The previously described key benzophenone KB may be engaged in a double Suzuki cross-coupling by reacting with a suitable electron-rich boronic acid/ester (either commercially available or not) in presence of a base and a palladium catalyst. The resulting extended benzophenone can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Dbis

[0439] Compounds of the formula D can also be obtained from the key methylene (KM) precursor prepared by the following Reaction Scheme 6bis:

##STR00044##

[0440] A meta-disubstituted phenol (either commercially available or not) is dimerized at its para position, in the presence of formaldehyde under acidic conditions (notably HCl, H.sub.2SO.sub.4 or AcOH), to give a diphenolmethane. Both hydroxy groups of the resulting compound are then triflated with triflic anhydride in the presence of pyridine to give the desired key methylene derivative, KM.

[0441] Compounds of the formula D (aryl extended ortho-substituted diphenylcarbenium) can be prepared from KM by the following Reaction Scheme 7bis, wherein X is an EDG:

##STR00045##

[0442] The previously described key methylene KM may be engaged in a double Suzuki cross-coupling by reacting with a suitable electron-rich boronic acid/ester (either commercially available or not) in the presence of a base and a palladium catalyst. The resulting extended methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure E

[0443] Compounds of the formula E can be obtained from the key benzophenone (KB) precursor prepared by the previously detailed Reaction Scheme 6.

[0444] Compounds of the formula E (julolidine extended ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 8, wherein X is an EDG:

##STR00046##

[0445] The key benzophenone precursor, KB, may be engaged in a double Suzuki cross-coupling by reacting with a julolidine moiety bearing a boronic acid/ester group in presence of a base and a palladium catalyst. The reacting julolidine is previously obtained from a classical Miyaura boration reaction on the bromojulolidine, itself synthesized according to a method described in the literature [Dance2008]. The resulting extended benzophenone can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Ebis

[0446] Compounds of the formula E can also be obtained from the key methylene (KM) precursor prepared by the previously detailed Reaction Scheme 6bis.

[0447] Compounds of the formula E (julolidine extended ortho-substituted diphenylcarbenium) can then be prepared by the following Reaction Scheme 8bis, wherein X is an EDG:

##STR00047##

[0448] The key methylene precursor, KM, may be engaged in a double Suzuki cross-coupling by reacting with a julolidine moiety bearing a boronic acid/ester group in the presence of a base and a palladium catalyst. The resulting extended methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure F

[0449] Compounds of the formula F can be obtained from the key benzophenone (KB) precursor prepared by the previously detailed Reaction Scheme 6.

[0450] Compounds of the formula F (p-X-substituted styryl extended ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 9, wherein X is an EDG:

##STR00048##

[0451] The key benzophenone KB may be engaged in a double Heck coupling by reacting with a p-EDG-substituted styryl precursor (either commercially available or not) in presence of a base and a palladium catalyst. The resulting extended benzophenone can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Fbis

[0452] Compounds of the formula F can also be obtained from the key methylene (KM) precursor prepared by the previously detailed Reaction Scheme 6bis.

[0453] Compounds of the formula F (p-X-substituted styryl extended ortho-substituted diphenylcarbenium) can then be prepared by the following Reaction Scheme 9bis, wherein X is an EDG:

##STR00049##

[0454] The key methylene KM may be engaged in a double Heck coupling by reacting with a p-EDG-substituted styryl precursor (either commercially available or not) in the presence of a base and a palladium catalyst. The resulting extended methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure G

[0455] Compounds of the formula G can be obtained from the key benzophenone (KB) precursor prepared by the previously detailed Reaction Scheme 6.

[0456] Compounds of the formula G (p-X-aryl ethynyl extended ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 10, wherein X is an EDG:

##STR00050##

[0457] The key benzophenone KB may be engaged in a double Sonogashira cross-coupling by reacting with an electron-rich p-EDG-substituted aryl ethynyl precursor (either commercially available or not) in presence of a base, Cu(I)-salt and a palladium catalyst. The resulting extended benzophenone can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Gbis

[0458] Compounds of the formula G can also be obtained from the key methylene (KM) precursor prepared by the previously detailed Reaction Scheme 6bis.

[0459] Compounds of the formula G (p-X-aryl ethynyl extended ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 10 Obis, wherein X is an EDG:

##STR00051##

[0460] The key methylene KM may be engaged in a double Sonogashira cross-coupling by reacting with an electron-rich p-EDG-substituted aryl ethynyl precursor (either commercially available or not) in presence of a base, Cu(I)-salt and a palladium catalyst. The resulting extended methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly an hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure H

[0461] Compounds of the formula H (hindered ipso-aryl ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 11, wherein X is an EDG:

##STR00052##

[0462] A meta-disubstituted electrodonating precursor (either commercially available or not) is engaged in a lithiation reaction. Depending on the nature of the starting material, a prior step of para bromination may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with diethyl carbonate yielding a benzophenone which is further engaged in presence of a hindered organolithium/Grignard reactant [Wu2008]. The tertiary alcohol intermediate thus obtained is itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure I

[0463] Compounds of the formula I (SiR.sub.2-bridged ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 12:

##STR00053##

[0464] A meta-brominated meta-substituted electrodonating precursor (either commercially available or not) is engaged in a formaldehyde-mediated dimerization reaction to give the corresponding dibromo diarylmethane [Koide2011]. The bromine atoms are then exchanged in presence of BuLi in order to produce the corresponding dilithium intermediate which is quenched by addition of a disubstituted silicon dichloride reagent [Koide2011]. The resulting bridged diarylmethane is then oxidized with DDQ or p-chloranil (or another suitable oxidant, which is here more particularly an hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis is required to obtain the desired counteranion (A.sup.).

General Procedure J

[0465] Compounds of the formula J (CMe.sub.2-bridged ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 13:

##STR00054##

[0466] A meta-brominated meta-substituted electrodonating precursor (either commercially available or not) is engaged in a halogen-metal exchange reaction to produce the corresponding lithiated intermediate which is quenched by addition of dry acetone. The resulting tertiary alcohol is then dehydrated by heating in presence of KHSO.sub.4 to give a methylene exo compound. The latter molecule is engaged with a closely related counterpart (but bearing a benzylic alcohol moiety) in a sequence of reactions allowing coupling and bridging of these two parts [Pastierik2014] and final oxidation with proper oxidant (e.g. KMnO.sub.4) to yield the totally symmetric CMe.sub.2-bridged benzophenone. This ketone is then reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure K

[0467] Compounds of the formula K (three and more atoms-bridged ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 14:

##STR00055##

[0468] A meta-methoxylated meta-substituted electrodonating precursor (either commercially available or not) is engaged in a lithiation reaction. Depending on the nature of the starting material, a prior step of para bromination may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with diethyl carbonate yielding a dimethoxy benzophenone, which methoxy groups are subsequently demethylated by using BBr.sub.3. The resulting phenol moieties are then bridged together through an aliphatic chain of length controlled by the nature of the reagent employed (e.g.: CH.sub.2BrCl for n=1, TsO(CH.sub.2).sub.2-OTs for n=2) [Sorrell1997]. The resulting bridged benzophenone can then be reduced (by either NaBH.sub.4 or LiAlH.sub.4) yielding the corresponding carbinol intermediate that can be itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

General Procedure Kbis

[0469] Compounds of the formula K (three and more atoms-bridged ortho-substituted diphenylcarbenium) can alternatively be prepared by the following Reaction Scheme 14bis:

##STR00056##

[0470] A meta-methoxylated meta-substituted electrodonating precursor (either commercially available or not) is engaged in the presence of a demethylating agent (e.g. BBr.sub.3 or TMSI) to give the corresponding phenol. The resulting compound was then dimerized at its para position, in the presence of formaldehyde under acidic conditions (notably HCl, H.sub.2SO.sub.4 or AcOH), to give a diphenolmethane. The hydroxyl groups are then bridged together through an aliphatic chain of length controlled by the nature of the reagent employed (e.g.: CH.sub.2BrCl for n=1, TsO(CH.sub.2).sub.2-OTs for n=2) [Sorrell1997]. The resulting bridged methylene can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly an hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

General Procedure L

[0471] Compounds of the formula L (hindered ipso-alkyl ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 15, wherein X is an EDG:

##STR00057##

[0472] A meta-disubstituted electrodonating precursor (either commercially available or not) is engaged in a lithiation reaction. Depending on the nature of the starting material, a prior step of para bromination may be necessary, employing either Br.sub.2 or NBS as reactive species [Zysman2009]. The lithiated intermediate is quenched with diethyl carbonate yielding a benzophenone which is further engaged in presence of an alkyl (either linear, branched or cyclic) organometallics. The tertiary alcohol intermediate thus obtained is itself easily dehydrated to produce the desired carbenium when reacted with acidic species (HA), the nature of which determines the identity of carbenium counteranion (A.sup.). The latter can be changed afterward by anion metathesis.

[0473] This procedure may be applied to acyclic or cyclic, substituted or unsubstituted alkyl groups.

[0474] Therefore, the substituent Alk in the above reaction scheme 15 encompasses (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, aryl-(C.sub.1-C.sub.6)alkyl, heteroaryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, cycloalkyl-(C.sub.1-C.sub.6)alkyl, heterocycle and heterocycle-(C.sub.1-C.sub.6)alkyl groups.

General Procedure M

[0475] Compounds of the formula M (hindered ipso-cyano ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 16, wherein X is an EDG:

##STR00058##

[0476] A methylium compound para-disubstituted with electrodonating groups X is engaged in a cyanation reaction, employing either KCN or another cyanide salt. The resulting neutral cyano compound can then be oxidized with DDQ (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis may optionally be required to obtain the desired counteranion (A.sup.).

[0477] References cited in the above described general procedures: [0478] [Zysman2009]: Zysman-Colman, E., Arias, K., Siegel, J. S. Can. J. Chem., 2009, 87, 440-447. [Patents]: CA 2311064; U.S. Pat. No. 6,670,512 [0479] [Torricelli2013]: Torricelli, F., Bosson, J., Besnard, C., Chekini, M., Biirgi, T., Lacour, J. Angew. Chem. Int. Ed. 2013, 52, 1796-1800. [0480] [Egawa2011]: Egawa, T., Koide, Y., Hanaoka, K., Komatsu, T., Terai, T., Nagano, T. Chem. Commun., 2011, 47, 4162-4164. [0481] [Takahashi2002]: Takahashi, H., Kashiwa, N., Hashimoto, Y., Nagasawa, K. Tetrahedron Lett. 2002, 43, 2935-2938. [0482] [Dance2008]: Dance, Z. E. X., Ahrens, M. J., Vega, A. M., Ricks, A. B., McCamant, D. W., Ratner, M. A., Wasielewski, M. R. J. Am. Chem. Soc. 2008, 130, 830-832. [0483] [Wu2008]: Wu, L., Burgess, K. J. Org. Chem. 2008, 73, 8711-8718. [0484] [Koide2011]: Koide, Y., Urano, Y., Hanaoka, K., Terai, T., Nagano, T. ACS Chem. Biol. 2011, 6, 600-608. [0485] [Sorrell1997]: Sorrell, T. N., Yuan, H. J. Org. Chem. 1997, 62, 1899-1902. [0486] [Pastierik2014]: Pastierik, T., ebej, P., Medalov, J., tacko, P., Kln, P. J. Org. Chem. 2014, 79, 3374-3382.

I-2. Examples of Syntheses of Compounds According to the Invention

I-2.i. Synthesis of Compounds 1, 2 and 3 According to General Procedure A

Compound 1-PF.SUB.6..SUP.

[0487] ##STR00059##

Bis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium hexafluorophosphate

[0488] To a solution of 3,5-dimethoxy-N,N-dimethylaniline (4.19 g, 23.15 mmol) in dry THF (40 mL) was added TMEDA (0.37 mL, 2.47 mmol, 0.1 equiv.). The solution was then cooled to 78 C., before dropwise addition of a 2.3 M n-BuLi solution in hexane (10.1 mL, 23.12 mmol, 1 equiv.). The suspension was stirred a few minutes at 78 C., then left to warm to room temperature and stirred for another 4 hours. The reaction mixture was then cooled to 78 C. and diluted with THF (60 mL) before dropwise addition of ethylformate (1.0 mL, 11.63 mmol, 0.48 equiv.). The mixture was stirred at room temperature under argon atmosphere overnight, then quenched with water and extracted with CH.sub.2Cl.sub.2. The organic layers were gathered, filtered on filter paper, and concentrated in vacuo without prior drying with MgSO.sub.4. The crude oil thus obtained was dissolved in a minimum amount of EtOH, before dropwise addition of acidic solution made up of an aqueous solution of HPF.sub.6 (60% in wt; 4.69 mL, 1.2 equiv.) diluted with EtOH (8 mL). To the dark blue solution was added a large amount of Et.sub.2O mixture (ca. 800 mL) whilst stirring vigorously. The supernatant was separated from the precipitate, which was dissolved in a minimum of MeCN (ca. 100 mL). To this solution was added a large amount of Et.sub.2O mixture (ca. 800 mL) whilst stirring vigorously. The dark blue precipitate was filtered off further purified by successive precipitation with Et.sub.2O from CH.sub.2Cl.sub.2 solutions to give the pure product. This compound was finally crystallized by slow vapor diffusion of Et.sub.2O into a MeCN solution of the chromophore (FIG. 2), affording shiny large columnar crystals with a gold-like metallic luster (FIGS. 4a, 4b and 4c) (2.14 g, 35.7% vs starting aniline derivative).

[0489] .sup.1H NMR (400 MHz, CD.sub.3CN): 3.25 (s, 12H, N(CH.sub.3).sub.2); 3.84 (s, 12H, OCH.sub.3); 5.90 (s, 4H, H.sub.3); 8.35 (s, 1H, H.sub.(C+)).

[0490] .sup.13C NMR (100 MHz, CD.sub.3CN): 41.5 (N(CH.sub.3).sub.2); 57.0 (OCH.sub.3); 89.6 (C.sub.3); 112.1 (C.sub.1); 143.4 (CH.sup.+); 160.4 (C.sub.4); 165.1 (C.sub.2).

[0491] M=518.4301 g.Math.mol.sup.1.

[0492] ESI-MS: m/z: calculated for C.sub.21H.sub.29N.sub.2O.sub.4: 373.2 [M-PF.sub.6].sup.+; found 373.2 [M-PF.sub.6].sup.+.

[0493] ESI-HRMS: m/z: calculated for C.sub.21H.sub.29N.sub.2O.sub.4: 373.2127 [M-PF.sub.6].sup.+; found 373.2139 [M-PF.sub.6].sup.+.

[0494] UV-vis-NIR (CH.sub.3CN) .sub.max/nm (/L mol.sup.1 cm.sup.1): 583 (88 000) (as can be seen in FIG. 1).

[0495] Crystal data: for C.sub.21.33H.sub.29.25F.sub.6N.sub.2.17O.sub.4P, monoclinic, P2.sub.1, a=15.2786(7), b=40.2601(16), c=24.1341(10) , =90.000, =102.7317(13), =90.000; V=14480.3, Z=24.

Compound 2-PF.SUB.6..SUP.

[0496] ##STR00060##

Bis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium hexafluorophosphate

[0497] To a solution of 3,5-dimethoxy-N,N-bis(4-methoxyphenyl)aniline (4.28 g, 11.7 mmol) in dry THF (20 mL) was added TMEDA (0.18 mL, 1.17 mmol, 0.1 equiv.). The solution was then cooled to 78 C., before dropwise addition of a 2.5 M n-BuLi solution in hexane (4.68 mL, 11.7 mmol, 1 equiv.). The suspension was stirred a few minutes at 78 C., then left to warm to room temperature and stirred for another 4 hours. The reaction mixture was then cooled to 78 C. and diluted with THF (40 mL) before dropwise addition of ethylformate (0.50 mL, 3.86 mmol, 0.5 equiv.). The mixture was stirred at room temperature under argon atmosphere overnight, then quenched with water and extracted with CH.sub.2Cl.sub.2. The organic layers were gathered, filtered on filter paper, and concentrated in vacuo without prior drying with MgSO.sub.4. The crude oil thus obtained was dissolved in a minimum amount of EtOH, before dropwise addition of an acidic solution made up of an aqueous solution of HPF.sub.6 (60% in wt; 2.4 mL, 1.2 equiv.) diluted with EtOH (8 mL). The dark blue-green solution was poured into a large amount of a Petroleum Ether/Et.sub.2O mixture (1:1 ratio; ca. 800 mL) whilst stirring vigorously. This operation was repeated as long as the supernatant remained green. The greenish-blue precipitate was filtered off and dissolved in a minimum amount of CH.sub.2Cl.sub.2 before being re-precipitated with a large amount of Et.sub.2O. The supernatant that contains the target product was separated from the solid (precipitate), which is essentially a by-product. The combined blue layers were concentrated under reduced pressure to afford the expected product as a dark blue solid. Several recrystallizations were performed from a CH.sub.2Cl.sub.2/Et.sub.2O mixture, giving the pure product as greenish iridescent crystalline plates with a bronze luster (FIG. 5) (0.622 g, 12% vs starting aniline derivative).

[0498] .sup.1H NMR (400 MHz, CD.sub.3CN): 3.59 (s, 12H, OCH.sub.3(C.sub.2)); 3.81 (s, 12H, OCH.sub.3(C.sub.4)); 5.81 (s, 4H, H.sub.3); 6.99-7.03 (m, 8H, H.sub.3); 7.25-7.29 (m, 8H, H.sub.2); 8.38 (s, 1H, H.sub.(C+)).

[0499] .sup.13C NMR (100 MHz, CD.sub.3CN): 56.3 (OCH.sub.3(C.sub.4)); 56.9 (OCH.sub.3(C.sub.2)); 93.0 (C.sub.3); 114.3 (C.sub.1); 116.2 (C.sub.3); 129.7 (C.sub.2); 137.6 (CH.sup.+); 145.0 (C.sub.1); 160.0 (C.sub.4); 161.2 (C.sub.4). 165.3 (C.sub.2).

[0500] M=886.8116 g.Math.mol.sup.1.

[0501] ESI-MS: m/z: calculated for C.sub.45H.sub.45N.sub.2O.sub.8: 741.3 [M-PF.sub.6].sup.+; found 741.3 [M-PF.sub.6].sup.+. ESI-HRMS: m/z: calculated for C.sub.45H.sub.45N.sub.2O.sub.8: 741.3176 [M-PF.sub.6].sup.+; found 741.3141 [M-PF.sub.6].sup.+.

[0502] UV-vis-NIR (CH.sub.3CN) .sub.max/nm (/L mol.sup.1 cm.sup.1): 630 (73 500) (as can be seen in FIG. 1).

[0503] Crystal data: for C.sub.45H.sub.45F.sub.6N.sub.2O.sub.8P, triclinic, P1, a=10.2521(3), b=10.7538(3), c=20.7783(6) , =95.3451(9), =98.3170(8), =108.9112(8); V=2120.21, Z=2.

Compound 3 Precursor

[0504] ##STR00061##

Bis(2,4,6-trimethoxyphenyl)methanol

[0505] To a solution of 1,3,5-trimethoxybenzene (5.50 g, 32.7 mmol) in THF (12 mL) was added hexane (5 mL) and TMEDA (0.49 mL, 3.27 mmol). To the solution thus obtained cooled at 78 C. was dropwise added a 2.5 M solution of n-butyllithium in hexane (15.7 mL, 39.2 mmol). The milky solution was stirred at room temperature for 4 h then cooled again at 78 C., diluted with THF (15 mL). To the cold solution was dropwise added ethylformate (1.32 mL, 1.64 mmol). The reaction mixture was stirred overnight at room temperature. To the solution cooled at 0 C. was added H.sub.2O (20 mL) and a 0.5 M aqueous solution of HCl (20 mL). The mixture was filtered off to afford the expected product as an off-white solid (1.135 g, 20%).

[0506] .sup.1H NMR (400 MHz, CDCl.sub.3): 3.75 (s, 12H, OCH.sub.3); 3.77 (s, 6H, OCH.sub.3); 5.39 (d, .sup.3J.sub.OHCH=10.29 Hz, 1H, OH); 6.09 (s, 4H, H.sub.3); 6.51 (d, .sup.3J.sub.5-OH=10.29 Hz, 1H, CH).

[0507] .sup.13C NMR (100 MHz, CDCl.sub.3): 55.3 (OCH.sub.3(C.sub.4)); 56.1 (OCH.sub.3(C.sub.2)); 64.1 (C.sub.3); 113.9 (C.sub.1); 159.1 (C.sub.2); 159.8 (C.sub.4).

[0508] ESI-MS: m/z: calculated for C.sub.19H.sub.24O.sub.7: 364.2 [M].sup.+; found 364.0 [M].sup.+.

Compound 3-PF6

[0509] ##STR00062##

Bis(2,4,6-trimethoxyphenyl)methylium hexafluorophosphate

[0510] To bis(2,4,6-trimethoxyphenyl)methanol (1.00 g, 2.75 mmol) dissolved in ethanol was dropwise added an aqueous solution of HPF.sub.6 (60% in wt, 0.5 mL). The colorless solution became dark red. A mixture (1:1 ratio) of petroleum ether and diethyl ether (200 mL) was added. The precipitate as a dark red solid was filtered off and was then dissolved in a minimum amount of acetone. A large amount of diethyl ether (500 mL) was added to this solution to give a dark red precipitate, which was filtered off. The solid was finally recrystallized from a mixture of CH.sub.2Cl.sub.2 and EtOAc, giving the pure expected product as dark-red needles with a slight silver-blue luster (0.773 g, 57%).

[0511] .sup.1H NMR (400 MHz, CD.sub.3CN): 3.94 (s, 12H, OCH.sub.3(C.sub.2)); 4.08 (m, 6H, OCH.sub.3(C.sub.4)); 6.26 (s, 4H, H.sub.3), 8.96 (s, 1H, H+).

[0512] .sup.13C NMR (100 MHz, CD.sub.3CN): 58.1 (OCH.sub.3(C.sub.2)); 58.4 (OCH.sub.3(C.sub.4)); 98.2 (C.sub.3); 116.3 (C.sub.1); 154.8 (CH.sup.+); 167.7 (C.sub.2), 176.6 (C.sub.4).

[0513] M=492.3465 g mol.sup.1.

[0514] UV-vis-NIR (CH.sub.3CN) .sub.max/nm (/L mol.sup.1 cm.sup.1): 518.5 (39 500).

[0515] Crystal data: for C.sub.19H.sub.23F.sub.6O.sub.6P, orthorhombic, Pbca, a=23.5779(7), b=7.3015(2), c=24.9654(7) , =90.000, =90.000, =90.000; V=4297.89, Z=8.

I-2.ii. Synthesis of Compounds 1, 2, and 27 to 31 According to General Procedure Abis

[0516] Synthesis of Diarylmethylene Precursors

[0517] General procedure: In a two-necked 50 mL round-bottom flask fitted with a reflux condenser, was placed a properly substituted aniline (6.7 mmol) diluted by addition of methanol (8 mL). Hydrochloric acid (0.34 mL, 37%) was then added dropwise to this solution, before addition of formalin (0.25 mL, 37% in water), and the resulting mixture was refluxed overnight under argon atmosphere. After completion of the reaction followed by TLC, the mixture was allowed to cool to room temperature and neutralized by slow addition of a 1M aqueous solution of NaHCO.sub.3 until pH 8 was reached. The mixture was then poured into 20 mL of distilled water and the resulting aqueous layer extracted three times with chloroform (340 mL). The organic layers were then combined, dried over MgSO.sub.4 and filtered before removal of the solvent under reduced pressure. The residue was finally purified by flash chromatography to give the target methylene compound that often easily crystallizes.

Compound 1 Precursor

[0518] ##STR00063##

4,4-methylenebis(3,5-dimethoxy-N,N-dimethylaniline)

[0519] The above general procedure was applied to 3,5-dimethoxy-N,N-dimethylaniline [Lee2009](3.11 g, 17.16 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-30% EtOAc/cyclohexane) and recrystallized as prismatic colorless crystals from a CH.sub.2Cl.sub.2/Et.sub.2O mixture (1.62 g, 50.3%).

[0520] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.94 (s, 4H, H.sub.3), 3.82 (s, 2H, CH.sub.2), 3.71 (s, 12H, OCH.sub.3), 2.90 (s, 12H, N(CH.sub.3).sub.2).

[0521] .sup.13C NMR (100 MHz, CDCl.sub.3) 159.5 (C.sub.2), 149.9 (C.sub.4), 109.8 (C.sub.1), 91.4 (C.sub.3), 56.4 (OCH.sub.3), 41.2 (N(CH.sub.3).sub.2), 16.6 (CH.sub.2).

[0522] HRMS: m/z: calcd for C.sub.21H.sub.30N.sub.2NaO.sub.4: 397.2098 [M+Na].sup.+; found: 397.2110 [M+Na].sup.+; calcd for C.sub.42H.sub.60N.sub.4NaO.sub.8: 771.4303 [2M+Na].sup.+; found: 771.4315 [2M+Na].sup.+.

Compound 2 Precursor

[0523] ##STR00064##

4,4-methylenebis(3,5-dimethoxy-N,N-bis(4-methoxyphenyl)aniline)

[0524] The above general procedure was applied to 3,5-dimethoxy-N,N-bis(4-methoxyphenyl)aniline [DellaPelle2014] (3.01 g, 8.24 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-10% EtOAc/cyclohexane) to give a white microcrystalline solid (0.75 g, 24.5%).

[0525] .sup.1H NMR (300 MHz, CDCl.sub.3): 7.10-6.98 (m, 8H, H.sub.2), 6.87-6.77 (m, 8H, H.sub.3), 6.16 (s, 4H, H.sub.3), 3.88 (s, 2H, CH.sub.2), 3.80 (s, 12H, OCH.sub.3(C.sub.4)), 3.56 (s, 12H, OCH.sub.3(C.sub.2)).

[0526] .sup.13C NMR (75 MHz, CDCl.sub.3): 159.1 (C2). 155.3 (C.sub.4), 147.2 (C.sub.4). 141.6 (C.sub.1), 126.0 (C.sub.2), 114.5 (C.sub.3), 113.2 (C.sub.1), 99.5 (C.sub.3), 56.1 (OCH.sub.3(C.sub.2)), 55.5 (OCH.sub.3(C.sub.4)), 17.1 (CH.sub.2).

[0527] HRMS: m/z: calcd for C.sub.45H.sub.46N.sub.2NaO.sub.8: 765.3146 [M+Na].sup.+; found: 765.3167 [M+Na].sup.+.

Compound 27 Precursor

[0528] ##STR00065##

Bis(2,6-dimethoxy-4-(piperidin-1-yl)phenyl)methane

[0529] The above general procedure was applied to 1-(3,5-dimethoxyphenyl)piperidine [L2011](3.91 g, 17.67 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-30% EtOAc/cyclohexane) and recrystallized as prismatic colorless crystals from a CH.sub.2Cl.sub.2/Et.sub.2O mixture (2.37 g, 59%).

[0530] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.13 (s, 4H, H.sub.3), 3.82 (s, 2H, CH.sub.2), 3.68 (s, 12H, OCH.sub.3), 3.08 (t, .sup.3J.sub.a-b=5.4 Hz, 8H, H.sub.a), 1.74-1.67 (m, 8H, H.sub.b), 1.59-1.51 (m, 4H, H.sub.c).

[0531] .sup.13C NMR (100 MHz, CDCl.sub.3) 159.2 (C.sub.2), 151.6 (C.sub.4), 112.1 (C.sub.1), 94.9 (C.sub.3), 56.3 (OCH.sub.3), 51.7 (C.sub.a), 26.2 (C.sub.b), 24.5 (C.sub.c), 16.9 (CH.sub.2).

[0532] HRMS: m/z: calcd for C.sub.27H.sub.39N.sub.2O.sub.4: 455.2904 [M+H].sup.+; found: 455.2922 [M+H].sup.+. Crystal data: for C.sub.27H.sub.38N.sub.2O.sub.4, monoclinic, C.sub.2/c, a=18.2443(6), b=13.1592(4), c=10.8058(3) , =90.000, =108.358(2), =90.000; V=2462.23, Z=4.

Compound 28 Precursor

[0533] ##STR00066##

Bis(2,6-dimethoxy-4-morpholinophenyl)methane

[0534] The above general procedure was applied to 4-(3,5-dimethoxyphenyl)morpholine [L2011](7.57 g, 33.90 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-30% EtOAc/cyclohexane) and recrystallized as prismatic colorless crystals from AcOEt (3.55 g, 45.7%).

[0535] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.09 (s, 4H, H.sub.3), 3.87-3.82 (m, 10H, H.sub.b+CH.sub.2), 3.69 (s, 12H, OCH.sub.3), 3.11 (t, .sup.3J.sub.a-b=4.8 Hz, 8H, H.sub.a).

[0536] .sup.13C NMR (100 MHz, CDCl.sub.3) 159.3 (C.sub.2), 150.5 (C.sub.4), 112.4 (C.sub.1), 93.8 (C.sub.3), 67.1 (H.sub.b), 56.2 (OCH.sub.3), 50.2 (H.sub.a), 16.8 (CH.sub.2).

[0537] HRMS: m/z: calcd for C.sub.25H.sub.35N.sub.2O.sub.6: 459.2490 [M+H].sup.+; found: 459.2502 [M+H].sup.+. Crystal data: for C.sub.25H.sub.34N.sub.2O.sub.6 (H.sub.2O).sub.0.25, monoclinic, P2/c, a=10.9761(8), b=13.8118(11), c=16.4099(11) , =90.000, =104.133(2), =90.000; V=2412.44, Z=4.

Compound 29 Precursor

[0538] ##STR00067##

4,4-methylenebis(N,N,3,5-tetramethylaniline)

[0539] The above general procedure was applied to commercially available N,N,3,5-tetramethylaniline (5.8 g, 38.86 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-30% EtOAc/cyclohexane) and recrystallized as prismatic colorless crystals from CH.sub.2Cl.sub.2/Et.sub.2O (5.31 g, 88%).

[0540] .sup.1H NMR (300 MHz, CDCl.sub.3) 6.41 (s, 4H, H.sub.3), 3.92 (s, 2H, CH.sub.2), 2.91 (s, 12H, N(CH.sub.3).sub.2), 2.11 (s, 12H, CH.sub.3).

[0541] .sup.13C NMR (75 MHz, CDCl.sub.3) 148.7 (C.sub.4), 137.6 (C.sub.2), 127.4 (C.sub.1), 113.6 (C.sub.3), 41.0 (N(CH.sub.3).sub.2), 30.1 (CH.sub.2), 21.5 (CH.sub.3).

[0542] HRMS: m/z: calcd for C.sub.21H.sub.31N.sub.2: 311.2482 [M+H].sup.+; found: 311.2480 [M+H].sup.+.

[0543] Crystal data: for C.sub.21H.sub.30N.sub.2, orthorhombic, Pbca, a=13.7462(4), b=12.3537(3), c=21.7385(6) , =90.000, =90.000, =90.000; V=3691.55(17), Z=8.

Compound 30 Precursor

[0544] ##STR00068##

Bis(2,6-dimethyl-4-(piperidin-1-yl)phenyl)methane

[0545] The above general procedure was applied to 1-(3,5-dimethylphenyl)piperidine [Hatakeyama2010] (7.30 g, 38.56 mmol). The title compound was purified by simply washing the crude product with Et.sub.2O and then recrystallized as prismatic colorless crystals from AcOEt (4.5 g, 59.8%).

[0546] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.58 (s, 4H, H.sub.3), 3.91 (s, 2H, CH.sub.2), 3.09 (t, .sup.3J.sub.a-b=5.4 Hz, 8H, H.sub.a), 2.08 (s, 12H, CH.sub.3), 1.75-1.66 (m, 8H, H.sub.b), 1.59-1.51 (m, 4H, H.sub.c).

[0547] .sup.13C NMR (100 MHz, CDCl.sub.3) 150.0 (C.sub.4), 137.5 (C.sub.2), 129.7 (C.sub.1), 117.2 (C.sub.3), 51.2 (C.sub.a), 30.4 (CH.sub.2), 26.1 (C.sub.b), 24.5 (C.sub.c), 21.4 (CH.sub.3).

[0548] HRMS: m/z: calcd for C.sub.27H.sub.39N.sub.2: 391.3108 [M+H].sup.+; found: 391.3104 [M+H].sup.+.

[0549] Crystal data: for C.sub.27H.sub.38N.sub.2, monoclinic, P2.sub.1/c, a=11.4761(5), b=21.1140(8), c=19.6436(9) , =90.000, =105.544(2), =90.000; V=4585.68, Z=8.

Compound 31 Precursor

[0550] ##STR00069##

Bis(2,6-dimethyl-4-morpholinophenyl)methane

[0551] The above general procedure was applied to 4-(3,5-dimethylphenyl)morpholine [Wolfe2000](5.13 g, 26.82 mmol). Crude product was washed with cyclohexane and recrystallized to afford the title compound as prismatic colorless crystals from CH.sub.2Cl.sub.2/Et.sub.2O (3.25 g, 61.4%).

[0552] .sup.1H NMR (400 MHz, CDCl.sub.3) 6.56 (s, 4H, H.sub.3), 3.93 (s, 2H, CH.sub.2), 3.86 (t, .sup.3J.sub.b-a=4.8 Hz, 8H, H.sub.b), 3.12 (t, .sup.3J.sub.a-b=4.8 Hz, 8H, H.sub.a), 2.10 (s, 12H, CH.sub.3).

[0553] .sup.13C NMR (100 MHz, CDCl.sub.3) 149.0 (C.sub.4), 137.8 (C.sub.2), 130.2 (C.sub.1), 116.3 (C.sub.3), 67.1 (C.sub.b), 49.8 (C.sub.a), 30.5 (CH.sub.2), 21.5 (CH.sub.3).

[0554] HRMS: m/z: calcd for C.sub.25H.sub.35N.sub.2O.sub.2: 395.2693 [M+H].sup.+; found: 395.2705 [M+H].sup.+.

[0555] Synthesis of Target Compounds from the Above Precursors:

[0556] General procedure for the synthesis of target compounds: To a vigorously stirred solution of the proper methylene compound in a minimum amount of THF was dropwise added a solution of oxidant (here more particularly an hydride abstraction reagent) in THF, preferably 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.0 equivalent). After stirring for approximately 2.5 h at room temperature, the reaction mixture was concentrated under reduced pressure and then dropwise added (after previous filtration through a pipette plugged with cotton wool) to a saturated solution of the desired counteranion, e.g. potassium hexafluorophosphate (metathesis of DDQH.sup./PF.sub.6.sup.). This suspension was stirred for 20 minutes before filtration of the dark precipitate, which was taken up in CH.sub.2Cl.sub.2. The resulting deeply (blue-)colored organic layer was washed with a minimum amount of distilled water (until giving a colorless aqueous layer) and concentrated under reduced pressure. The residue was finally purified by slow vapor crystallization. Noticingly, the final metathesis may be avoided to afford the methylium compound associated to a counteranion derived from the reduced form of the oxidant sooner utilized, e.g. DDQH.sup..

Compound 27-DDQH.SUP.

[0557] ##STR00070##

Bis(2,6-dimethoxy-4-(piperidin-1-yl)phenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate

[0558] The above general procedure for the synthesis of target compounds was applied to the previously described bis(2,6-dimethoxy-4-(piperidin-1-yl)phenyl)methane (2.48 g, 5.45 mmol) to yield the title compound that was simply filtered from the reaction mixture to give a shiny microcrystalline solid (affording a blue solution) (2.79 g, 75%) that was recrystallized from CH.sub.3CN/Et.sub.2O as greenish iridescent crystalline plates with a bronze luster.

[0559] .sup.1H NMR (300 MHz, DMSO-d.sub.6) 8.13 (s, 1H, CH.sup.+), 6.13 (s, 4H, H.sub.3), 3.82 (s, 12H, OCH.sub.3), 3.77-3.65 (m, 8H, H.sub.a), 1.76-1.57 (m, 12H, H.sub.b+H.sub.c).

[0560] .sup.13C NMR (75 MHz, DMSO-d.sub.6) 163.9 (C.sub.2), 158.0 (C.sub.4), 140.1 (CH.sup.+), 111.0 (C.sub.1), 89.2 (C.sub.3), 56.4 (OCH.sub.3), 48.6 (C.sub.a), 25.9 (C.sub.b), 23.8 (C.sub.c).

Compound 27-PF.SUB.6..SUP.

[0561] ##STR00071##

Bis(2,6-dimethoxy-4-(piperidin-1-yl)phenyl)methylium hexafluorophosphate

[0562] A small quantity (1.79 g, 2.64 mmol) of the previously described bis(2,6-dimethoxy-4-(piperidin-1-yl)phenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxy-phenolate was engaged in a metathesis step using potassium hexafluorophosphate The title compound was purified by discarding remaining impurities loosely soluble in CH.sub.2Cl.sub.2 and recrystallized by slow diffusion of Et.sub.2O in a concentrated CH.sub.3CN solution to yield the desired carbenium as greenish iridescent crystalline plates with a bronze luster (1.0 g, 63.3%).

[0563] .sup.1H NMR (400 MHz, CD.sub.3CN) 8.26 (s, 1H, CH.sup.+), 6.03 (s, 4H, H.sub.3), 3.82 (s, 12H, OCH.sub.3), 3.71-3.66 (m, 8H, H.sub.a), 1.76-1.68 (m, 12H, H.sub.b+H.sub.c).

[0564] .sup.13C NMR (100 MHz, CDCl.sub.3) 165.4 (C.sub.2), 159.5 (C.sub.4), 142.2 (CH.sup.+), 112.5 (C.sub.1), 90.2 (C.sub.3), 57.0 (OCH.sub.3), 49.9 (C.sub.a), 26.9 (C.sub.b), 24.9 (C.sub.c).

[0565] HRMS (ESI+): m/z: calcd for C.sub.27H.sub.37N.sub.2O.sub.4: 453.2748 [M-PF.sub.6].sup.+; found: 453.2745 [M-PF.sub.6].sup.+.

[0566] HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0529 [PF.sub.6].sup..

[0567] UV-vis-NIR (CH.sub.3CN) max/nm (/L mol.sup.1 cm.sup.1): 592 (92 419) (as can be seen in FIG. 6).

Compound 28-PF.SUB.6..SUP.

[0568] ##STR00072##

Bis(2,6-dimethoxy-4-morpholinophenyl)methylium hexafluorophosphate

[0569] The above general procedure for the synthesis of target compounds was applied to bis(2,6-dimethoxy-4-morpholinophenyl)methane (1.00 g, 2.18 mmol). The title compound was purified by discarding remaining impurities loosely soluble in CH.sub.2Cl.sub.2 and recrystallized by slow diffusion of Et.sub.2O in a concentrated CH.sub.3CN solution to yield the desired carbenium as shiny large columnar crystals with a green metallic luster (1.02 g, 77.7%).

[0570] .sup.1H NMR (300 MHz, CD.sub.3CN) 8.34 (s, 1H, CH.sup.+), 6.04 (s, 4H, H.sub.3), 3.84 (s, 12H, OCH.sub.3), 3.82-3.77 (dd, .sup.3J.sub.a-b=4.5 Hz, 8H, H.sub.b), 3.69-3.65 (dd, .sup.3J.sub.b-a=4.5 Hz, 8H, H.sub.a).

[0571] .sup.13C NMR (100 MHz, CDCl.sub.3) 165.5 (C.sub.2), 160.4 (C.sub.4), 143.7 (CH.sup.+), 113.3 (C.sub.1), 90.4 (C.sub.3), 67.1 (C.sub.b), 57.1 (OCH.sub.3), 48.7 (C.sub.a).

[0572] HRMS (ESI+): m/z: calcd for C.sub.25H.sub.33N.sub.2O.sub.6: 457.2333 [M-PF.sub.6].sup.+; found: 457.2351 [M-PF.sub.6].sup.+.

[0573] HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0727 [PF.sub.6].sup..

[0574] UV-vis-NIR (CH.sub.3CN) max/nm (/L mol.sup.1 cm.sup.1): 586 (79 860) (as can be seen in FIG. 6).

[0575] Crystal data: for C.sub.25H.sub.33F.sub.6N.sub.2O.sub.6P.CH.sub.3CN, monoclinic, P2.sub.1/c, a=12.2406(3), b=16.9800(3), c=15.1295(3) , =90.000, =109.7300(10), =90.000; V=2959.9, Z=4.

Compound 29-DDQH.SUP.

[0576] ##STR00073##

Bis(4-(dimethylamino)-2,6-dimethylphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate

[0577] The above general procedure for the synthesis of target compounds was applied to 4,4-methylenebis(N,N,3,5-tetramethylaniline) (5.99 g, 19.29 mmol) to yield the title compound that was simply filtered from the reaction mixture to give a brown solid (affording a blue solution) (7.0 g, 67.5%) that that appears under microscope as shiny tiny crystals with a gold-like metallic luster.

[0578] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.35 (s, 1H, CH.sup.+), 6.77 (s, 4H, H.sub.3), 3.27 (s, 12H, N(CH.sub.3).sub.2), 2.20 (s, 12H, CH.sub.3).

[0579] .sup.13C NMR (100 MHz, DMSO-d.sub.6) 155.8 (CH.sup.+), 155.7 (C.sub.4), 145.9 (C.sub.2), 128.8 (C.sub.1), 114.2 (C.sub.3), 40.6 (N(CH.sub.3).sub.2), 21.2 (CH.sub.3).

[0580] HRMS (ESI+): m/z: calcd for C.sub.21H.sub.29N.sub.2: 309.2325 [M-DDQH].sup.+; found: 309.2313 [M-DDQH].sup.+.

[0581] HRMS (ESI): m/z: calcd for C.sub.8HCl.sub.2N.sub.2O.sub.2: 226.9421 [DDQH].sup.; found: 227.1023 [DDQH].sup..

Compound 29-PF.SUB.6..SUP.

[0582] ##STR00074##

Bis(4-(dimethylamino)-2,6-dimethylphenyl)methylium hexafluorophosphate

[0583] A small quantity (2.0 g, 3.73 mmol) of the previously described bis(4-(dimethylamino)-2,6-dimethylphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate was engaged in a metathesis step using potassium hexafluorophosphate. The crude product was washed with chloroform and AcOEt and recrystallized from CH.sub.2Cl.sub.2/Et.sub.2Ot to give the title compound as shiny large crystalline plates with a gold-like metallic luster (1.1 mg, 65%).

[0584] .sup.1H NMR (300 MHz, CD.sub.3CN) 8.39 (s, 1H, CH.sup.+), 6.67 (s, 4H, H.sub.3), 3.23 (s, 12H, N(CH.sub.3).sub.2), 2.22 (s, 12H, CH.sub.3).

[0585] .sup.13C NMR (100 MHz, CD.sub.3CN) 157.8 (CH.sup.+), 157.4 (C.sub.4), 147.8 (C.sub.2), 130.2 (C.sub.1), 115.2 (C.sub.3), 41.4 (N(CH.sub.3).sub.2), 21.8 (CH.sub.3).

[0586] HRMS (ESI+): m/z: calcd for C.sub.21H.sub.29N.sub.2: 309.2325 [M-PF.sub.6].sup.+; found: 309.2333 [M-PF.sub.6].sup.+.

[0587] HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0845 [PF.sub.6].sup..

[0588] UV-vis-NIR (CH.sub.3CN) max/nm (/L mol.sup.1 cm.sup.1): 644 (46 507) (as can be seen in FIG. 6).

[0589] Crystal data: for C.sub.21H.sub.29F.sub.6N.sub.2P, triclinic, P1, a=11.4808(6), b=17.1376(10), c=18.2833(11) , =110.738(2), =92.232(2), =98.955(2); V=3305.95, Z=6. [0590] Compound 30-PF.sub.6.sup.:

##STR00075##

Bis(2,6-dimethyl-4-(piperidin-1-yl)phenyl)methylium hexafluorophosphate

[0591] The above general procedure for the synthesis of target compounds was applied to bis(2,6-dimethyl-4-(piperidin-1-yl)phenyl)methane (2.60 g, 6.66 mmol). The crude product was washed with EtOAc to give the title compound as greenish iridescent crystalline plates with a bronze luster (2.0 g, 56.2%).

[0592] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.26 (s, 1H, CH.sup.+), 6.82 (s, 4H, H.sub.3), 3.68-3.62 (m, 8H, H.sub.a), 2.19 (s, 12H, CH.sub.3), 1.76-1.69 (m, 12H, H.sub.b,c).

[0593] .sup.13C NMR (100 MHz, CDCl.sub.3) 156.6 (CH.sup.+), 156.0 (C.sub.4), 147.5 (C.sub.2), 131.1 (C.sub.1), 116.2 (C.sub.3), 50.5 (C.sub.a), 27.0 (C.sub.b), 24.8 (C.sub.c), 21.8 (CH.sub.3).

[0594] HRMS (ESI+): m/z: calcd for C.sub.27H.sub.37N.sub.2: 389.2951 [M-PF.sub.6].sup.+; found: 389.2948 [M-PF.sub.6].sup.+.

[0595] HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0831 [PF.sub.6].sup..

[0596] UV-vis-NIR (CH.sub.3CN) max/nm (/L mol.sup.1 cm.sup.1): 655.5 (31 067) (as can be seen in FIG. 6).

Compound 31-PF.SUB.6..SUP.

[0597] ##STR00076##

Bis(2,6-dimethyl-4-morpholinophenyl)methylium hexafluorophosphate

[0598] The above general procedure for the synthesis of target compounds was applied to bis(2,6-dimethyl-4-morpholinophenyl)methane (2.35 g, 5.96 mmol). The title compound was purified by discarding remaining impurities loosely soluble in CH.sub.2Cl.sub.2 and by washing the resulting crude product with a THF/Et.sub.2O mixture to yield a lustrous solid (1.5 g, 46.7%).

[0599] .sup.1H NMR (300 MHz, CD.sub.3CN) 8.35 (s, 1H, CH.sup.+), 6.82 (s, 4H, H.sub.3), 3.85-3.78 (m, 8H, H.sub.b), 3.64-3.59 (m, 8H, H.sub.a), 2.21 (s, 12H, CH.sub.3).

[0600] .sup.13C NMR (75 MHz, CDCl.sub.3) 157.6 (C.sub.4), 157.1 (CH.sup.+), 147.6 (C.sub.2), 131.8 (C.sub.1), 116.3 (C.sub.3), 67.2 (C.sub.b), 49.4 (C.sub.a), 21.8 (CH.sub.3).

[0601] HRMS (ESI+): m/z: calcd for C.sub.25H.sub.33N.sub.2O.sub.2: 393.2537 [M-PF.sub.6].sup.+; found: 393.2526 [M-PF.sub.6].sup.+; calcd for C.sub.26H.sub.37N.sub.2O.sub.3: 425.2799 [M-PF.sub.6+MeOH].sup.+; found: 425.2772 [M-PF.sub.6+MeOH].sup.+. HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0865 [PF.sub.6].sup..

I-2.iii. Synthesis of Compounds 8 and 11 According to General Procedure Cbis

[0602] Synthesis of Julolidine-Type Diarylmethylene Precursors

[0603] General procedure: in a two-necked 50 mL round-bottom flask fitted with a reflux condenser, was placed a properly substituted aniline (7.65 mmol) diluted by addition of a 17 mL MeCN/CH.sub.2Cl.sub.2/H.sub.2O (12:4:1) mixture. Hydrochloric acid (0.25 mL, 37%) was then added dropwise to this solution, before addition of formalin (0.25 mL, 37% in water), and the resulting mixture was refluxed overnight under argon atmosphere. After completion of the reaction followed by TLC, the mixture was allowed to cool to room temperature and neutralized by slow addition of a 1M aqueous solution of NaHCO.sub.3 until pH 8 was reached. The mixture was then poured into 20 mL of distilled water and the resulting aqueous layer extracted three times with chloroform (340 mL). The organic layers were then combined, dried over MgSO.sub.4 and filtered before removal of the solvent under reduced pressure. The residue was finally purified by flash chromatography to give the target methylene compound that often easily crystallizes.

Compound 8 Precursor

[0604] ##STR00077##

Bis(8,10-dimethoxy-2,3,6,7-tetrahydro-1H, 5H-pyrido[3,2,1-ij]quinolin-9-yl) methane

[0605] The above general procedure was applied to 8,10-dimethoxyjulolidine [U.S. Pat. No. 4,471,041] (0.50 g, 2.14 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 40-100% CH.sub.2Cl.sub.2/cyclohexane then 0-10% EtOAc/CH.sub.2Cl.sub.2) and recrystallized as prismatic colorless crystals from CH.sub.2Cl.sub.2/Et.sub.2O (0.23 g, 45%).

[0606] .sup.1H NMR (300 MHz, CDCl.sub.3) 3.90 (s, 2H, CH.sub.2), 3.49 (s, 12H, OCH.sub.3), 3.07 (t, .sup.3J.sub.a-b=5.7 Hz, 8H, H.sub.a), 2.72 (t, .sup.3J.sub.c-b=6.6 Hz, 8H, H.sub.c), 1.96-1.86 (m, 8H, H.sub.b).

[0607] .sup.13C NMR (75 MHz, CDCl.sub.3) 155.5 (C.sub.2), 142.1 (C.sub.4), 116.5 (C.sub.1), 111.2 (C.sub.3), 60.1 (OCH.sub.3), 50.3 (C.sub.a), 22.1 (C.sub.c), 21.8 (C.sub.b), 19.1 (CH.sub.2).

[0608] HRMS: m/z: calcd for C.sub.29H.sub.38N.sub.2NaO.sub.4: 501.2724 [M+Na].sup.+; found: 501.2737 [M+Na].sup.+. Crystal data: for C.sub.29H.sub.38N.sub.2O.sub.4, orthorhombic, Pbca, a=17.4380(4), b=9.0985(2), c=31.4390(8) , =90.000, =90.000, =90.000; V=4988.1, Z=8.

Compound 11 Precursor

[0609] ##STR00078##

Bis(8,10-dimethyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methane

[0610] The above general procedure was applied to 8,10-dimethyljulolidine [Dance2008] (1.54 g, 7.65 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 30-100% CH.sub.2Cl.sub.2/cyclohexane then 0-15% EtOAc/CH.sub.2Cl.sub.2) (0.54 g, 34%).

[0611] .sup.1H NMR (400 MHz, CDCl.sub.3) 4.03 (s, 2H, CH.sub.2), 3.02 (t, .sup.3J.sub.a-b=5.4 Hz, 8H, H.sub.a), 2.64 (t, .sup.3J.sub.c-b=6.8 Hz, 8H, H.sub.c), 2.04-1.98 (m, 8H, H.sub.b), 1.97 (s, 12H, CH.sub.3).

[0612] .sup.13C NMR (100 MHz, CDCl.sub.3) 142.0 (C.sub.4), 133.0 (C.sub.2), 129.0 (C.sub.1), 119.0 (C.sub.3), 50.5 (C.sub.a), 32.2 (CH.sub.2), 26.2 (C.sub.c), 23.1 (C.sub.b), 16.2 (CH.sub.3).

[0613] HRMS: m/z: calcd for C.sub.29H.sub.39N.sub.2: 415.3108 [M+H].sup.+; found: 415.3115 [M+H].sup.+.

[0614] Synthesis of Julolidine-Type Diarylmethylene Target Compounds:

[0615] General procedure for the synthesis of target compounds is the same as in the previous section: To a vigorously stirred solution of the proper methylene compound in a minimum amount of THF was dropwise added a solution of oxidant (here more particularly an hydride abstraction reagent) in THF, preferably 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.0 equivalent). After stirring for approximately 2.5 h at room temperature, the reaction mixture was concentrated under reduced pressure and then dropwise added (after previous filtration through a pipette plugged with cotton wool) to a saturated solution of the desired counteranion, e.g. potassium hexafluorophosphate (metathesis of DDQH.sup./PF6.sup.). This suspension was stirred for 20 minutes before filtration of the dark precipitate, which was taken up in CH.sub.2Cl.sub.2. The resulting deeply (blue-)colored organic layer was washed with a minimum amount of distilled water (until giving a colorless aqueous layer) and concentrated under reduced pressure. The residue was finally purified by slow vapor crystallization. Noticingly, the final metathesis may be avoided to afford the methylium compound associated to a counteranion derived from the reduced form of the oxidant sooner utilized, e.g. DDQH.sup..

Compound 8-PF.SUB.6..SUP.

[0616] ##STR00079##

Bis(8,10-dimethoxy-2,3,6,7-tetrahydro-1H, 5H-pyrido[3,2,1-ij]quinolin-9-yl)methylium hexafluorophosphate

[0617] The general procedure as above was applied to bis(8,10-dimethoxy-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methane (0.23 g, 0.48 mmol) to give pure title compound as a lustrous solid after several recrystallizations (0.045 g, 15%).

[0618] .sup.1H NMR (300 MHz, CD.sub.3CN) 8.29 (s, 1H, CH.sup.+), 3.69 (s, 12H, OCH.sub.3), 3.56-3.49 (m, 8H, H.sub.a), 2.81-2.74 (m, 8H, H.sub.c), 2.14-2.09 (m, 8H, H.sub.b).

Compound 11-PF.SUB.6..SUP.

[0619] ##STR00080##

Bis(8,10-dimethyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methylium hexafluorophosphate

[0620] The general procedure as above was applied to bis(8,10-dimethyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij]quinolin-9-yl)methane (0.5 g, 1.20 mmol) to give pure title compound as a lustrous solid after several recrystallizations (0.134 g, 20%).

[0621] .sup.1H NMR (300 MHz, CD.sub.3CN) 8.26 (s, 1H, CH.sup.+), 3.48-3.41 (m, 8H, H.sub.a), 2.71-2.63 (m, 8H, H.sub.c), 2.04 (s, 12H, CH.sub.3), 2.03-1.91 (m, 8H, H.sub.b).

[0622] HRMS (ESI+): m/z: calcd for C.sub.29H.sub.37N.sub.2: 413.2951 [M-PF.sub.6].sup.+; found: 413.2959 [M-PF.sub.6].

[0623] HRMS (ESI): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.; found: 145.0901 [PF.sub.6].sup..

I-2.iv. Synthesis of Compounds 32 According to General Procedure M

[0624] Synthesis of Diarylcyanomethylene Precursors

[0625] General procedure for the synthesis of precursors: To a vigorously stirred solution of the proper methylium compound in a minimum amount of MeCN was portionwise added KCN (or another cyanide salt) (1.0 equivalent). After stirring for approximately 3-4 h at room temperature, the resulting colorless reaction mixture was filtered if appearance of a precipitate and then concentrated under reduced pressure. The residue was taken up in CH.sub.2Cl.sub.2 and the organic layer washed with distilled water before concentration under reduced pressure to give the target compound with no need of further purification.

Compound 32 Precursor

[0626] ##STR00081##

2,2-Bis(4-(dimethylamino)-2,6-dimethoxyphenyl)acetonitrile

[0627] The above general procedure was applied to bis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium hexafluorophosphate (0.279 g, 0.54 mmol) to yield the title compound as colorless microcrystals (0.213 g, 99%).

[0628] .sup.1H NMR (400 MHz, CDCl.sub.3) 5.87 (s, 4H, H.sub.3), 5.86 (s, 1H, CH), 3.77 (s, 12H, OCH.sub.3), 2.93 (s, 12H, N(CH.sub.3).sub.2).

[0629] .sup.13C NMR (100 MHz, CDCl.sub.3) 159.1 (C.sub.2), 151.2 (C.sub.4), 121.7 (CN), 103.4 (C.sub.1), 90.3 (C.sub.3), 56.2 (OCH.sub.3), 40.8 (N(CH.sub.3).sub.2), 21.3 (CH).

[0630] HRMS: m/z: calcd for C.sub.22H.sub.29N.sub.3NaO.sub.4: 422.2050 [M+Na].sup.+; found: 422.2064 [M+Na].sup.+; calcd for C.sub.44H.sub.58N.sub.6NaO.sub.8: 821.4208 [2M+Na].sup.+; found: 821.4268 [2M+Na].sup.+.

[0631] Synthesis of Diarylcyanomethyliums Target Compounds

[0632] General procedure for the synthesis of target diarylcyanomethyliums: To a vigorously stirred solution of the proper cyanomethylene compound in a minimum amount of THF was dropwise added a solution of oxidant (here more particularly an hydride abstraction reagent) in THF, preferably 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (1.0 equivalent). After stirring for approximately 2.5 h at room temperature, the reaction mixture was concentrated under reduced pressure and then dropwise added (after previous filtration through a pipette plugged with cotton wool) to a saturated solution of the desired counteranion, e.g. potassium hexafluorophosphate (metathesis of DDQH.sup./PF.sub.6.sup.). This suspension was stirred for 20 minutes before filtration of the dark precipitate, which was taken up in CH.sub.2Cl.sub.2. The resulting deeply (green-)colored organic layer was washed with a minimum amount of distilled water (until giving a colorless aqueous layer) and concentrated under reduced pressure. The residue can finally be further purified by slow vapor crystallization. Noticingly, the final metathesis may be avoided to afford the methylium compound associated to a counteranion derived from the reduced form of the oxidant sooner utilized, e.g. DDQH.sup..

Compound 32-DDQH.SUP.

[0633] ##STR00082##

Cyanobis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate

[0634] The above general procedure for the synthesis of target diarylcyanomethyliums was applied to 2,2-bis(4-(dimethylamino)-2,6-dimethoxyphenyl)-acetonitrile (0.2 g, 0.50 mmol) to yield the title compound that was simply filtered from the reaction mixture to give a reddish brown solid (affording a green solution) that appears under microscope as shiny tiny crystals with a gold-like metallic luster (0.220 g, 70.3%).

[0635] .sup.1H NMR (300 MHz, DMSO-d.sub.6) 6.06 (s, 4H, H.sub.3), 3.80 (s, 12H, OCH.sub.3), 3.37 (s, 12H, N(CH.sub.3).sub.2).

[0636] .sup.13C NMR (75 MHz, DMSO-d.sub.6) 161.5 (C.sub.2), 157.9 (C.sub.4), 118.4 (CN.sub.DDQH), 117.0 (CN.sub.DDQH), 115.7 (C.sub.1), 90.4 (C.sub.3), 56.6 (OCH.sub.3), 41.4 (N(CH.sub.3).sub.2).

[0637] HRMS (ESI+): m/z: calcd for C.sub.22H.sub.28N.sub.3O.sub.4: 398.2074 [M-DDQH].sup.+; found: 398.2088 [M-DDQH].sup.+.

[0638] HRMS (ESI): m/z: calcd for C.sub.8HCl.sub.2N.sub.2O.sub.2: 226.9421 [DDQH].sup.; found: 226.0912 [DDQH].sup..

Compound 32-PF.SUB.6..SUP.

[0639] ##STR00083##

Cyanobis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium hexafluorophosphate

[0640] A small quantity of the previously described cyanobis(4-(dimethylamino)-2,6-dimethoxyphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (50 mg, 0.08 mmol) was engaged in a metathesis step using potassium hexafluorophosphate. The crude product was washed with chloroform to give the title compound as iridescent crystalline plates with a copper-like metallic luster (30 mg, 69%).

[0641] .sup.1H NMR (300 MHz, CD.sub.3CN) 5.94 (s, 4H, H.sub.3), 3.79 (s, 12H, OCH.sub.3), 3.29 (s, 12H, N(CH.sub.3).sub.2).

[0642] .sup.13C NMR (75 MHz, CD.sub.3CN) 163.3 (C.sub.2), 159.9 (C.sub.4), 117.4 (C.sub.1), 91.1 (C.sub.3), 57.1 (OCH.sub.3), 42.0 (N(CH.sub.3).sub.2).

[0643] HRMS (ESI+): m/z: calcd for C.sub.22H.sub.28N.sub.3O.sub.4: 398.2074 [M-PF.sub.6].sup.+; found: 398.2085 [M-PF.sub.6].sup.+.

[0644] HRMS (ESI): m/z: cal cd for F.sub.6P: 144.9647 [PF.sub.6].sup.. found: 145.0862 [PF.sub.6].sup..

[0645] UV-vis-NIR (CH.sub.3CN) max/nm (/L mol.sup.1 cm.sup.1): 704.5 (33 444) (as can be seen in FIG. 6).

[0646] References reporting the preparation and characterization of some starting materials used in the above described general procedures: [0647] [Lee2009]: Lee, B. K., Biscoe, M. R., Buchwald, S. L. Tetrahedron Lett., 2009, 50, 3672-3674. [0648] [DellaPelle2014]: Della Pelle, A. M., Homnick, P. J., Bae, Y., Lahti, P. M., Thayumanavan, S. J. Phys. Chem. C, 2014, 118, 1793-1799. [0649] [Yang1999]: Yang, S.-C., Hung, C.-W. Synthesis, 1999, 10, 1747-1752. [0650] [L2011] L, B., Li, P., Fu, C., Xue, L., Lin, Z., Ma, S. Adv. Synth. Catal., 2011, 353, 100-112. [0651] [Hatakeyama2010]: Hatakeyama, T., Yoshimoto, Y., Ghorai, S. K., Nakamura, M. Org. Lett., 2010, 12, 1516-1519. [0652] [Wolfe2000]: Wolfe, J. P., Tomori, H., Sadighi, J. P., Jin, J., Buchwald, S. L. J. Org. Chem., 2000, 65, 1158-1174. [0653] [Saitoh2004] Saitoh, T., Yoshida, S., Ichikawa, J. Org. Lett., 2004, 6, 4563-4565. [U.S. Pat. No. 4,471,041] [0654] [Dance2008]: Dance, Z. E. X., Ahrens, M. J., Vega, A. M., Ricks, A. B., McCamant, D. W., Ratner, M. A., Wasielewski, M. R. J. Am. Chem. Soc. 2008, 130, 830-832.

IIOptical Properties of the Compounds According to the Invention

II-1. Absorption Properties

[0655] Measurement of the molar extinction coefficients of compounds 1-PF.sub.6.sup., 2-PF.sub.6.sup., 27-PF.sub.6.sup., 28-PF.sub.6.sup., 29-PF.sub.6.sup., 30-PF.sub.6.sup. and 32-PF.sub.6.sup. was carried as follows: for each compound, three independent 10.sup.5 mol.Math.L.sup.1 acetonitrile solutions (200 mL) were prepared, and absorbances were measured in a 1 cm optical path quartz cuvettes (against reference 1 cm optical path quartz cuvette containing pure acetonitrile) in a double-beam Cary 500 spectrophotometer (Varian).

[0656] As it appears on FIGS. 1 and 6, the compounds according to the invention are characterized by a single sharp absorption band in the visible region of the electromagnetic spectrum, and a high molar extinction coefficient. Appropriate chemical modulations allow the absorption bands of the compounds according to the invention to span over an extended region of the visible electromagnetic spectrum (hence allowing display of numerous metal-like effects).

[0657] Accordingly, chromophoric properties of compounds of the invention are directly observed from these solutions. For example, an intense deep blue color is observed for 1-PF.sub.6.sup., 27-PF.sub.6.sup. and 28-PF.sub.6.sup. dissolved in acetonitrile, whereas an intense deep green color is observed for 32-PF.sub.6.sup. dissolved in the same solvent (not shown).

II-2. Other Optical Properties

[0658] FIG. 3 represents a photograph of the gold-like reflective mirror formed on the wall of a round-bottom flask after simple evaporation of a concentrated solution of 1-PF.sub.6.sup. in acetonitrile, hence showing the propensity of the molecule to self-assemble to yield a well-shaped coating that displays optical properties of interest (e.g. obtaining of a reflective metal-like luster). [0659] FIG. 4a represents a photograph (macroscopic view) of typical microcrystalline sample of 1-PF.sub.6.sup., showing a golden-like glittering/sparkling behavior to the naked eye. [0660] FIGS. 4b and 4c represent micrographs of typical single crystals of compound 1-PF.sub.6.sup., taken under non-polarized light. FIG. 4b shows the hexagonal shape of gold-like reflective single crystals. [0661] FIG. 5 represents a micrograph of typical polycrystalline aggregates of greenish-blue chromophore 2-PF.sub.6.sup. exhibiting the iridescent behavior of the crystals observed to the naked eye (under non-polarized light). [0662] FIGS. 7a and 7b are micrographs of typical greenish iridescent crystalline plates of compound 27-DDQH.sup. exhibiting the bronze luster of the crystals observed to the naked eye (under non-polarized light). [0663] FIGS. 8a and 8b are micrographs of typical greenish iridescent crystalline plates of compound 27-PF.sub.6.sup. exhibiting the bronze luster of the crystals observed to the naked eye (under non-polarized light). [0664] FIGS. 9a and 9b are micrographs of typical large columnar crystals of compound 28-PF.sub.6.sup., taken under non-polarized light. FIG. 9b shows the hexagonal shape of green reflective single crystals. [0665] FIGS. 10a and 10b are micrographs showing typical tiny crystals of compound 29-DDQH.sup. showing a golden-like glittering/sparkling behavior to the naked eye (under non-polarized light). [0666] FIGS. 11a and 11b are micrographs of typical large crystalline plates of compound 29-PF.sub.6.sup. exhibiting the gold luster of the crystals observed to the naked eye (under non-polarized light). FIGS. 12a and 12b are micrographs of typical greenish iridescent crystalline plates of compound 30-PF.sub.6.sup. exhibiting the bronze luster of the crystals observed to the naked eye (under non-polarized light). [0667] FIGS. 13a and 13b are micrographs showing typical tiny crystals of compound 32-DDQH.sup. displaying a golden-like glittering/sparkling behavior to the naked eye (under non-polarized light). [0668] FIGS. 14a and 14b are micrographs of typical iridescent crystalline plates of compound 32-PF.sub.6.sup. exhibiting the copper luster of the crystals observed to the naked eye (under non-polarized light). [0669] Elaboration and characterization of films made of compounds of the invention: spin coating and quantitative reflectance measurements

[0670] The compounds according to the invention are soluble in most organic polar solvents. For example, an acetonitrile (CH.sub.3CN) solution of a compound of the invention (for example at a concentration of 1 mg/mL) can be prepared.

[0671] This solution is spin-coated onto a substrate, and after solvent evaporation under ambient conditions, a uniform film exhibiting a reflective appearance is obtained.

[0672] Films of different thicknesses can be spin-coated by varying the spin-coating speed or acceleration or duration, or by varying the volume of the solution that is deposited onto the substrate. Also, several layers of films can be superimposed by repeating successive steps of spin coating as above.

[0673] Doctor blade technique may also represent an alternative and efficient mode of preparation of films made of compounds of the invention.