Amphiphilic and Mesogenic Organic Dyes for Tailor-Made Reflective Low-Dimensional Materials

Abstract

The present invention relates to a compound of the following formula (I):

##STR00001##

The invention also relates to uses thereof as dye or pigment, notably as a luster pigment. The invention relates also to a reflective or photonic or nanophotonic or optoelectronic device comprising a compound of the invention. The invention relates also to a metal-like reflective coating, a metal-like particle or an organic-based metal-like liquid film comprising a compound of the invention.

Claims

1. A compound of following general formula (I): ##STR00089## 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, COR.sub.11, CO.sub.2R.sub.12, CONR.sub.13R.sub.14, SO.sub.2R.sub.15, CN or NO.sub.2, group, or is selected from the group consisting of: ##STR00090## 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 hydrogen atom, a halogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.1-C.sub.20)haloalkyl, aryl, heteroaryl, aryl-(C.sub.1-C.sub.6)alkyl, cycloalkyl, 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.20)alkyl, (C.sub.1-C.sub.20)haloalkyl, cycloalkyl, heterocycle or O(C.sub.1-C.sub.20)alkyl group; R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.2-C.sub.12)alkynyl, (C.sub.1-C.sub.20)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, COR.sub.32, OCOR.sub.36 or NR.sub.38COR.sub.39 group, wherein m and m′ are, independently of each other, equal to 1, 2 or 3, preferably 1; R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.2-C.sub.12)alkynyl, (C.sub.1-C.sub.20)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.m′SR.sub.25, OR.sub.26, SR.sub.27, NR.sub.28R.sub.29, COR.sub.32, OCOR.sub.36 or NR.sub.38COR.sub.39 group, wherein m and m′ are, independently of each other, equal to 1, 2 or 3, preferably 1; or both R.sub.4 groups form together a bond or a chain selected from the group consisting of —C(R.sub.42R.sub.43)—, —(CH.sub.2).sub.n—, —Si(R.sub.44R.sub.45)—, —CH.sub.2—Y—CH.sub.2—, and —Y—CH.sub.2—CH.sub.2—Y′—, wherein: Y and Y′ each represent, independently of each other, O, S or NH, n is equal to 2 or 3, R.sub.42 and R.sub.43, each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl or an aryl group, and R.sub.44 and R.sub.45 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl or an aryl group; L represents a bond, or a group selected from the group consisting of: ##STR00091## 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.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.49 or NR.sub.51R.sub.52 group; or L represents: ##STR00092## and R.sub.f and R.sub.2, and R.sub.g and R.sub.3 form together with the carbon atoms that carry them a cycloalkenyl or aryl group; R.sub.N and R.sub.N′ each represent, independently of each other, a (C.sub.7-C.sub.20)alkyl or (C.sub.7-C.sub.20)haloalkyl group, said group being optionally substituted by one or more groups selected from OR.sub.62, SR.sub.63 and NR.sub.64R.sub.65, or a group selected from the group consisting of: ##STR00093## wherein: X represents O, S or NR.sub.57, Y represents OR.sub.58, SR.sub.59 or NR.sub.60 R.sub.61, x is equal to 0, 1, 2 or 3, preferably x is equal to 1, 2 or 3, y is equal to 0, 1, 2 or 3, z is equal to 0, 1, 2 or 3, R.sub.k and R.sub.l each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, R.sub.m represents a (C.sub.1-C.sub.20)alkyl group, R.sub.r represents a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, R.sub.p and R.sub.q each represent, independently of each other, a hydrogen atom, a (C.sub.1-C.sub.6)alkyl, an aryl or heteroaryl group, R.sub.57 to R.sub.65 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; R.sub.5 to R.sub.8, R.sub.11 to R.sub.15, R.sub.24, R.sub.25, R.sub.28, R.sub.29, R.sub.32, R.sub.36, R.sub.38, R.sub.39, R.sub.49; R.sub.51 and R.sub.52 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, preferably a hydrogen atom or a (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.64, SR.sub.65 and NR.sub.66R.sub.67 group, wherein R.sub.64 to R.sub.67 each represent, independently of each other, a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; R.sub.22, R.sub.23, R.sub.26 and R.sub.27 each represent, independently of each other a hydrogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.1-C.sub.20)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, preferably a hydrogen atom or a (C.sub.1-C.sub.20)alkyl, notably (C.sub.1-C.sub.12)alkyl, in particular (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.66, SR.sub.67 and NR.sub.68R.sub.69 group, wherein R.sub.66 to R.sub.69 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, organic or inorganic anion, with the proviso that when R.sub.1 and R.sub.4 are the same, and R.sub.0 is: ##STR00094## wherein Z represents C, at least one of R.sub.a and R.sub.e is not the same as R.sub.1.

2. The compound according to claim 1, wherein R.sub.N═R.sub.N′.

3. The compound according to claim 1 or 2, 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, cycloalkyl, heterocycle, OR.sub.5, SR.sub.6, NR.sub.7R.sub.8, CN, or NO.sub.2 group, or is selected from the group consisting of: ##STR00095## 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, hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, 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 or (C.sub.1-C.sub.6)haloalkyl group, with the proviso that when R.sub.1 and R.sub.4 are the same, and R.sub.0 is: ##STR00096## wherein Z represents C, at least one of R.sub.a and R.sub.e is not the same as R.sub.1.

4. The compound according to claim 3, 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, CN or NO.sub.2 group, or is: ##STR00097## wherein: Z represents C, R.sub.a and R.sub.e each represent, independently of each other, a hydrogen atom, a halogen atom, a (C.sub.1-C.sub.6)alkyl or (C.sub.1-C.sub.6)haloalkyl group, and R.sub.b, R.sub.c and R.sub.d each represent a hydrogen atom, preferably R.sub.0 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl or a CN group, notably a hydrogen atom or a CN group.

5. The compound according to any one of claims 1 to 4, wherein R.sub.1 represents a halogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.1-C.sub.20)haloalkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27 or NR.sub.28R.sub.29 group, wherein m and m′ are, independently of each other, equal to 1, 2 or 3, preferably 1.

6. The compound according to any one of claims 1 to 5, wherein: R.sub.4 represents a halogen atom, a (C.sub.1-C.sub.20)alkyl, (C.sub.1-C.sub.20)haloalkyl, (CH.sub.2).sub.mOR.sub.24, (CH.sub.2).sub.mSR.sub.25, OR.sub.26, SR.sub.27 or NR.sub.28R.sub.29 group wherein m and m′ are, independently of each other, equal to 1, 2 or 3, preferably 1; or both R.sub.4 groups form together a bond or a chain selected from the group consisting of —C(R.sub.42R.sub.43)—, —(CH.sub.2).sub.n—, —Si(R.sub.44R.sub.45)— and —Y—CH.sub.2—CH.sub.2—Y′—, wherein: Y and Y′ each represent, independently of each other, O, S or NH, n is equal to 2 or 3, R.sub.42 and R.sub.43, each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl group, and R.sub.44 and R.sub.45 each represent, independently of each other, a (C.sub.1-C.sub.6)alkyl group.

7. The compound according to any one of claims 1 to 6, wherein L represents a bond.

8. The compound according to any one of claims 1 to 7, wherein 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 or (C.sub.1-C.sub.6)haloalkyl group, notably a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, preferably R.sub.2 and R.sub.3 both represent a hydrogen atom.

9. The compound according to any one of claims 1 to 8, wherein R.sub.1═R.sub.4 and/or R.sub.2═R.sub.3 and/or R.sub.a═R.sub.e.

10. The compound according to any one of claims 1 to 9, wherein it is chosen from the following compounds: ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108##

11. The compound according to any one of claims 1 to 10, wherein A.sup.− represents a hexafluorophosphate, tetrafluoroborate, tetraphenylborate, 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (DDQH.sup.−), halide or triflate anion, preferably a DDQH.sup.− or hexafluorophosphate anion.

12. Use as dye or pigment of a compound as defined in any one of claims 1 to 11, notably as a luster pigment.

13. A reflective or photonic or nanophotonic or optoelectronic device, characterized in that it comprises at least one compound as defined in any one of claims 1 to 11.

14. An organic-based metal-like liquid film (OMELLF), characterized in that it comprises at least one compound as defined in any one of claims 1 to 11.

15. A metal-like reflective coating or a metal-like particle, characterized in that it comprises at least one compound as defined in any one of claims 1 to 11.

Description

FIGURES

[0312] FIG. 1 represents the absorption spectra of compounds 5-PF.sub.6.sup.−, 11-PF.sub.6.sup.− and 12-PF.sub.6.sup.− in solution in acetonitrile.

[0313] FIG. 2 corresponds to a picture of a magenta-colored liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 1-DDQH.sup.−, into a stirred saturated aqueous solution of KPF.sub.6.

[0314] FIG. 3 corresponds to a picture of a magenta-colored mirror of compound 1-PF.sub.6.sup.− that forms on the glass wall of a container, resulting from evaporation of a concentrated acetonitrile solution of chromophoric compound 1-PF.sub.6.sup.−.

[0315] FIG. 4 represents a photograph of a magenta reflective film covering a PTFE magnetic stir bar and its retriever after dipping into the solution displaying at the air-liquid interface the liquid mirror illustrated in FIG. 2.

[0316] FIG. 5 represents a macroscopic view of compound 5-DDQH.sup.− in its solid form, characterized by its reddish copper flakes appearance.

[0317] FIG. 6 represents a microscopic view of compound 5-DDQH.sup.− in its solid form, characterized by its metallic and copper/gold flakes appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0318] FIG. 7 corresponds to a picture of a gold-like liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 5-DDQH.sup.− into a stirred saturated aqueous solution of KPF.sub.6.

[0319] FIG. 8 corresponds to a picture of a self-assembled gold-like liquid mirror observed few minutes after dropwise addition of an acetonitrile solution of compound 5-PF.sub.6.sup.− onto the surface of a saturated aqueous solution of NaCl.

[0320] FIG. 9 corresponds to a picture of a copper/gold-like mirror of compound 5-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 5-PF.sub.6.sup.−.

[0321] FIG. 10 represents a macroscopic view of compound 5-PF.sub.6.sup.− in its polycrystalline form, characterized by its green metallic luster appearance.

[0322] FIG. 11 represents a microscopic view of compound 5-PF.sub.6.sup.− in its polycristalline form, obtained with a Zeiss-Stemi 2000-C microscope.

[0323] FIG. 12 displays a microscopic view of compound 11-PF.sub.6.sup.− in its microcrystallized form, characterized by its dual metallic (copper/gold & bronze/green) appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0324] FIG. 13 corresponds to a picture of a copper/gold-like mirror of compound 11-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 11-PF.sub.6.sup.−.

[0325] FIG. 14 corresponds to a picture of the outside view of a bronze-like mirror of compound 11-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 11-PF.sub.6.sup.−.

[0326] FIG. 15 displays a microscopic view of compound 11-DDQH.sup.− in its microcrystallized form, characterized by its greenish gold luster appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0327] FIG. 16 displays a macroscopic view of compound 12-PF.sub.6.sup.− in its solid form, characterized by its dual magenta/copper luster appearance.

[0328] FIG. 17 corresponds to a picture of a magenta-like mirror of compound 12-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 12-PF.sub.6.sup.−.

[0329] FIG. 18 corresponds to a picture of the outside view of a copper-like mirror of compound 12-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 12-PF.sub.6.sup.−.

[0330] FIG. 19 corresponds to a picture of a purple liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 33-DDQH.sup.−, into a stirred saturated aqueous solution of KPF.sub.6.

[0331] FIG. 20 represents a macroscopic view of compound 34-DDQH.sup.− in form of a metallic pink lacquer.

[0332] FIG. 21 corresponds to a picture of a magenta/pink-colored liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 34-DDQH.sup.−, into a stirred saturated aqueous solution of KPF.sub.6.

[0333] FIG. 22 represents a photograph of a magenta/pink reflective film covering a PTFE magnetic stir bar and its retriever after dipping into the solution displaying at the air-liquid interface the liquid mirror illustrated in FIG. 21.

[0334] FIG. 23 represents a macroscopic view of compound 34-PF.sub.6.sup.− in its solid form, characterized by its reddish copper flakes appearance.

[0335] FIG. 24 corresponds to a picture of a magenta/blue-like mirror of compound 34-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophore compound 34-PF.sub.6.sup.−.

[0336] FIG. 25 corresponds to a picture of the outside view of a copper-like mirror of compound 34-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated acetonitrile solution of chromophoric compound 34-PF.sub.6.sup.−.

[0337] FIG. 26 corresponds to a picture of a reflective layer of compound 35-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask, resulting from the evaporation under reduced pressure of a concentrated dichloromethane solution of chromophore compound 35-PF.sub.6.sup.−.

[0338] The examples that follow illustrate the invention without limiting its scope in any way.

EXAMPLES

[0339] The following abbreviations have been used: [0340] Ac: Acetyl (COCH.sub.3) [0341] All: Allyl [0342] Bn: Benzyl (CH.sub.2Ph) [0343] Bu: Butyl (CH.sub.2CH.sub.2CH.sub.2CH.sub.3) [0344] ca.: circa [0345] DDQ: 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone [0346] DCM: Dichloromethane [0347] DMF: Dimethylformamide [0348] equiv.: equivalent [0349] ESI: Electrospray ionisation [0350] Et: Ethyl (CH.sub.2CH.sub.3) [0351] LAH: Lithium aluminium hydride [0352] Me: Methyl (CH.sub.3) [0353] MS: Mass Spectroscopy [0354] NBS: N-Bromosuccinimide [0355] NIR: Near Infra Red [0356] NMR: Nuclear Magnetic Resonance [0357] Ph: Phenyl (C.sub.6H.sub.5) [0358] PPA: Polyphosphoric acid [0359] PTFE: Polytetrafluoroethylene [0360] Tf.sub.2O: Triflic anhydride [0361] THF: Tetrahydrofuran [0362] TMSI: Trimethylsilyl iodide [0363] vis: visible [0364] wt: weight

I—Synthesis of the Compounds According to the Invention

I-1. General Procedures

[0365] General Procedure A:

[0366] Compounds of the formula A (para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 1:

##STR00045##

[0367] A meta-disubstituted N,N-disubstituted aniline 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.

[0368] General Procedure Abis:

[0369] Compounds of the formula A (para-amino 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)):

##STR00046##

[0370] A meta-disubstituted N,N-disubstituted aniline 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.−).

[0371] General Procedure B:

[0372] Compounds of the formula B ((polyalkoxyphenyl)-para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 3:

##STR00047##

[0373] Commercially available 5-bromo-1,2,3-trimethoxybenzene is engaged in a demethylation reaction mediated by BBr.sub.3 to give 5-bromo-1,2,3-triol. This trihydroxybenzene is then engaged in a Williamson etherification with alkyl halides of desired length. Resulting bromotrialkoxybenzene is coupled with an adequately substituted aniline either under Ullmann [Velasco2009] or Buchwald-Hartwig [Rajan2012] conditions. This precursor can then be engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002]. The resulting methylene 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.−).

[0374] General Procedure Bbis:

[0375] Compounds of the formula B ((polyalkoxyphenyl)-para-amino ortho-substituted diphenylcarbenium) can also be prepared by the following Reaction Scheme 3bis:

##STR00048##

[0376] A meta-disubstituted aniline (either commercially available or not) is engaged in a diallylation step [Egawa2011]. This protected aniline can then be engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002], before deprotection of the allyl groups (e.g. by using a palladium catalyst in presence of 1,3-dimethylbarbituric acid) [Egawa2011]. The resulting diaminophenyl methylene is then coupled with a bromotrialkoxybenzene compound either under Ullmann [Velasco2009] or Buchwald-Hartwig [Rajan2012] conditions. The resulting methylene 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.−).

[0377] General Procedure C:

[0378] Compounds of the formula C ((polyalkoxybenzyl)-para-amino ortho-substituted diphenylcarbenium) can also be prepared by the following Reaction Scheme 4:

##STR00049##

[0379] Commercially available methyl gallate is engaged in a Williamson etherification with alkyl halides of desired length. Resulting trialkoxyphenylester is reduced (e.g. with lithium aluminium hydride) into the corresponding benzylic alcohol. This latter is then chlorinated in presence of SOCl.sub.2 [Balagurusamyl997], before its coupling, under basic conditions, with an adequately substituted aniline. This precursor can then be engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002]. The resulting methylene 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.−).

[0380] General Procedure Cbis:

[0381] Compounds of the formula C ((polyalkoxybenzyl)-para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 4bis:

##STR00050##

[0382] A meta-disubstituted aniline (either commercially available or not) is engaged in a diallylation step [Egawa2011]. This protected aniline can then be engaged in a formaldehyde-mediated dimerization reaction [Takahashi2002], before deprotection of the allyl groups (e.g. by using a palladium catalyst in presence of 1,3-dimethylbarbituric acid) [Egawa2011]. The resulting diaminophenyl methylene is then coupled with a trialkoxybenzyl chloride compound under basic conditions. The resulting methylene 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.−).

[0383] General Procedure D:

[0384] Compounds of the formula D can be obtained from the key benzophenone (KB) precursor prepared by the following Reaction Scheme 5:

##STR00051##

[0385] 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 derivatives, KB.

[0386] Compounds of the formula D (para-(aryl-extended amino) ortho-substituted diphenylcarbenium) can then be prepared by the following Reaction Scheme 6:

##STR00052##

[0387] The previously described key benzophenone KB precursors may be engaged in a double Suzuki cross-coupling by reacting with a para-aminophenylboronic 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.

[0388] General Procedure Dbis:

[0389] Compounds of the formula D can also be obtained from the key methylene (KM) precursors prepared by the following Reaction Scheme 7:

##STR00053##

[0390] A meta-disubstituted phenol (either commercially available or not) is dimerized at its para position, in the presence of formaldehyde either under basic or 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 derivatives, KM.

[0391] Compounds of the formula D (para-(aryl-extended amino) ortho-substituted diphenylcarbenium) can be prepared from KM precursors by the following Reaction Scheme 6bis:

##STR00054##

[0392] The previously described key methylene KM precursors may be engaged in a double Suzuki cross-coupling by reacting with a para-aminophenylboronic 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.−).

[0393] General Procedure E:

[0394] Compounds of the formula E can be obtained from the key benzophenone (KB) precursors prepared by the previously detailed Reaction Scheme 5.

[0395] Compounds of the formula E (para-(styryl-extended amino) ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 8:

##STR00055##

[0396] The key benzophenone KB precursors may be engaged in a double Heck coupling by reacting with a para-aminostyryl 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.

[0397] General Procedure Ebis:

[0398] Compounds of the formula E can also be obtained from the key methylene (KM) precursors prepared by the previously detailed Reaction Scheme 7.

[0399] Compounds of the formula E (para-(styryl-extended amino) ortho-substituted diphenylcarbenium) can then be prepared by the following Reaction Scheme 8bis:

##STR00056##

[0400] The key methylene KM may be engaged in a double Heck coupling by reacting with a para-aminostyryl 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.−).

[0401] General Procedure F:

[0402] Compounds of the formula F can be obtained from the key benzophenone (KB) precursors prepared by the previously detailed Reaction Scheme 5.

[0403] Compounds of the formula F (para-(phenylethynyl-extended amino) ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 9:

##STR00057##

[0404] The key benzophenone KB precursors may be engaged in a double Sonogashira cross-coupling by reacting with a para-aminophenethynyl 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 LiAH.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.

[0405] General Procedure Fbis:

[0406] Compounds of the formula F can also be obtained from the key methylene (KM) precursors prepared by the previously detailed Reaction Scheme 7.

[0407] Compounds of the formula F (para-(phenylethynyl-extended amino) ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 9bis:

##STR00058##

[0408] The key methylene KM may be engaged in a double Sonogashira cross-coupling by reacting with a para-aminophenethynyl 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 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.−).

[0409] General Procedure G:

[0410] Compounds of the formula G (hindered ipso-aryl para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 10:

##STR00059##

[0411] A meta-disubstituted N,N-disubstituted aniline 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.

[0412] General Procedure Gbis:

[0413] Compounds of the formula G (hindered ipso-aryl para-amino ortho-substituted diphenylcarbenium) can alternatively be prepared by the following Reaction Scheme 10bis:

##STR00060##

[0414] A meta-disubstituted N,N-disubstituted aniline 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 further engaged in presence of a conveniently substituted aryl ester. 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.

[0415] General Procedure H:

[0416] Compounds of the formula H (SiR.sub.2-bridged para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 11:

##STR00061##

[0417] A meta-brominated meta-substituted aniline 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 a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis is required to obtain the desired counteranion (A.sup.−).

[0418] General Procedure I:

[0419] Compounds of the formula I (CMe.sub.2-bridged para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 12:

##STR00062##

[0420] A meta-bromo N,N-disubstituted aniline 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]. The resulting bridged diarylmethane is then oxidized with DDQ or p-chloranil (or another suitable oxidant, which is here more particularly a hydride abstraction reagent) to directly produce the desired carbenium. A final step of metathesis is required to obtain the desired counteranion (A.sup.−).

[0421] General Procedure J:

[0422] Compounds of the formula J (three and more atoms-bridged para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 13:

##STR00063##

[0423] A meta-methoxylated N,N-disubstituted aniline precursor 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.

[0424] General Procedure Jbis:

[0425] Compounds of the formula J (three and more atoms-bridged para-amino ortho-substituted diphenylcarbenium) can alternatively be prepared by the following Reaction Scheme 13bis:

##STR00064##

[0426] A meta-methoxylated N,N-disubstituted aniline 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 is 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 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.−).

[0427] General Procedure K:

[0428] Compounds of the formula K (hindered ipso-alkyl para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 14:

##STR00065##

[0429] A meta-disubstituted N,N-disubstituted aniline 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.

[0430] General Procedure L:

[0431] Compounds of the formula L (hindered ipso-cyano para-amino ortho-substituted diphenylcarbenium) can be prepared by the following Reaction Scheme 15:

##STR00066##

[0432] A bis(para-aminophenyl)methylium compound 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.−).

REFERENCES CITED IN THE ABOVE DESCRIBED GENERAL PROCEDURES

[0433] [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 [0434] [Takahashi2002]: Takahashi, H., Kashiwa, N., Hashimoto, Y., Nagasawa, K. Tetrahedron Lett. 2002, 43, 2935-2938. [0435] [Velasco2009] Velasco, D., Jankauskas, V., Stumbraite, J., Grazulevicius, J. V., Getautis, V. Synth. Met., 2009, 159, 654-658. [0436] [Rajan2012] Rajan, Y. C., Shellaiah, M., Huang, C.-T., Lin, H.-C., Lin, H.-C. Tetrahedron, 2012, 68, 7926-7931. [0437] [Egawa2011] Egawa, T., Koide, Y., Hanaoka, K., Komatsu, T., Terai, T., Nagano, T. Chem. Commun., 2011, 47, 4162-4164. [0438] [Balagurusamyl997] Balagurusamy, V. S. K., Ungar, G., Percec, V., Johansson, G. J. Am. Chem. Soc., 1997, 119, 1539-1555. [0439] [Torricelli2013]: Torricelli, F., Bosson, J., Besnard, C., Chekini, M., Burgi, T., Lacour, J. Angew. Chem. Int. Ed. 2013, 52, 1796-1800. [0440] [Koide2011]: Koide, Y., Urano, Y., Hanaoka, K., Terai, T., Nagano, T. ACS Chem. Biol. 2011, 6, 600-608. [0441] [Pastierik2014]: Pastierik, T., Sebej, P., Medalovi, J., tacko, P., Klin, P. J. Org. Chem. 2014, 79,3374-3382. [0442] [Sorrell1997]: Sorrell, T. N., Yuan, H. J. Org. Chem. 1997, 62, 1899-1902. [0443] [Best2013] Best, Q. A., Sattenapally, N., Dyer, D. J., Scott, C. N., McCarroll, M. E. J. Am Chem. Soc. 2013, 135, 13365-13370. [0444] [Pastierik2014]: Pastierik, T., Sebej, P., Medalovi, J., tacko, P., Klin, P. J. Org. Chem. 2014, 79,3374-3382. [0445] [Sorrell1997]: Sorrell, T. N., Yuan, H. J. Org. Chem. 1997, 62, 1899-1902. [0446] [Singh2014] Singh, D., Chaudhari, U. V., Deota P. T. Tetrahedron, 2014, 70, 4485-4493.

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

Method 1: General Procedure for Synthesis of Diarylmethylene Precursors

[0447] 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 (3×40 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.

[0448] Compound 1 Precursor-1 (Procedure Abis):

##STR00067##

[0449] To a suspension of K.sub.2CO.sub.3 (10.83 g, 78.5 mmol) in MeCN (80 mL) was added 3,5-dimethoxyaniline (2.0 g, 13.06 mmol) under argon, and the reaction mixture was stirred for 1 h at room temperature. After iodooctane (12.53 g, 52.2 mmol) was added, the mixture was refluxed for 24 h under stirring. The reaction mixture was then allowed to cool to room temperature, filtered through a pad of celite and concentrated under reduced pressure. The crude mixture was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-20% CH.sub.2Cl.sub.2/petroleum ether) to afford the expected product as a greenish oil (4.26 g, 87%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.84 (br s, 3H, H.sub.1+H.sub.3), 3.77 (s, 6H, OCH.sub.3), 3.24-3.18 (m, 4H, H.sub.a), 1.62-1.53 (m, 4H, H.sub.b), 1.36-1.23 (m, 20H, H.sub.c-g), 0.92-0.85 (m, 6H, H.sub.h). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 161.8 (C.sub.2), 150.1 (C.sub.4), 91.3 (C.sub.3), 87.3 (C), 55.1 (OCH.sub.3), 51.3 (Ca), 31.9 (C.sub.b), 29.6 (CC), 29.4 (C.sub.d), 27.5 (Ce), 27.3 (C.sub.f), 22.7 (C.sub.g), 14.1 (C.sub.h). HRMS: m/z: calcd for C.sub.24H.sub.44NO.sub.2: 378.3367 [M+H].sup.+; found: 378.3359 [M+H].sup.+.

[0450] Compound 1 Precursor-2 (Procedure Abis):

##STR00068##

[0451] The method 1 was applied to 3,5-dimethoxy-N,N-dioctylaniline (4.17 g, 11.04 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-10% CH.sub.2Cl.sub.2/cyclohexane) to afford a greenish oil (2.96 g, 69.5%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.85 (s, 4H, H.sub.3), 3.76 (s, 2H, CH.sub.2), 3.69 (s, 12H, OCH.sub.3), 3.22-3.16 (m, 8H, H.sub.a), 1.61-1.55 (m, 8H, H.sub.b), 1.32-1.27 (m, 40H, H.sub.c-g), 0.90-0.87 (m, 12H, H.sub.h). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 159.7 (C.sub.2), 147.5 (C.sub.4), 108.7 (C.sub.1), 91.0 (C.sub.3), 56.4 (OCH.sub.3), 51.5 (C.sub.a), 32.0 (C.sub.b), 29.7 (C.sub.c), 29.5 (C.sub.d), 27.6 (C.sub.e), 27.4 (C.sub.f), 22.8 (C.sub.g), 16.5 (CH.sub.2), 14.2 (C.sub.h). HRMS: m/z: calcd for C.sub.49H.sub.87N.sub.2O.sub.4: 767.6660 [M+H].sup.+; found: 767.6662 [M+H].sup.+.

[0452] Compound 5 Precursor-1 (Procedure Abis):

##STR00069##

[0453] To a suspension of K.sub.2CO.sub.3 (10.06 g, 72.47 mmol) and NaI (1.09 g, 7.25 mmol) in DMF (55 mL) was added under argon 3,5-dimethoxyaniline (5.05 g, 32.94 mmol), and 2-chloroethyl methyl ether (6.06 mL, 66.54 mmol). The mixture was heated at 90° C. for 12 h under stirring. The reaction mixture was then allowed to cool to room temperature, filtered through a pad of celite and concentrated under reduced pressure. The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-5% EtOAc/cyclohexane) to afford the expected product as a colorless oil (5.7 g, 64.3%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.91 (d, .sup.4J.sub.3-1=2.0 Hz, 2H, H.sub.3), 5.88 (t, .sup.3J.sub.1-3=2.0 Hz, 1H, H.sub.1), 3.77 (s, 6H, .sup.2OCH.sub.3), 3.54 (m, 8H, H.sub.a,b), 3.35 (s, 6H, .sup.bOCH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 161.9 (C.sub.2), 149.9 (C.sub.4), 91.6 (C.sub.3), 88.4 (C.sub.1), 70.4 (C.sub.b), 59.1 (.sup.bOCH.sub.3), 55.3 (.sup.2OCH.sub.3), 51.4 (Ca). HRMS: m/z: calcd for C.sub.14H.sub.23NO.sub.4Na: 292.1519 [M+Na].sup.+; found: 292.1520 [M+Na].sup.+.

[0454] Compound 5 Precursor-2 (Procedure Abis):

##STR00070##

[0455] The method 1 was applied to 3,5-dimethoxy-N,N-bis(2-methoxyethyl)aniline (2.21 g, 8.22 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-20% EtOAc/cyclohexane) (1.44 g, 64%). .sup.1H NMR (300 MHz, CDCl.sub.3) δ 5.92 (s, 4H, H.sub.3), 3.78 (s, 2H, CH.sub.2), 3.69 (s, 12H, .sup.2OCH.sub.3), 3.54-3.49 (m, 16H, H.sub.a,b), 3.35 (s, 12H, .sup.bOCH.sub.3). .sup.13C NMR (75 MHz, CDCl.sub.3) δ 159.7 (C.sub.2), 147.1 (C.sub.4), 109.3 (C.sub.1), 90.9 (C.sub.3), 70.6 (OCH.sub.2), 59.1 (.sup.bOCH.sub.3), 56.4 (.sup.2OCH.sub.3), 51.5 (NCH.sub.2), 16.4 (CH.sub.2). HRMS: m/z: calcd for C.sub.29H.sub.47N.sub.2O.sub.8: 551.3327 [M+H].sup.+; found: 551.3324 [M+H].sup.+.

[0456] Compound 11Precursor (Procedure Abis):

##STR00071##

[0457] The method 1 was applied to N,N-diallyl-3,5-dimethoxyaniline [Yang1999] (3.0 g, 12.85 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-10% CH.sub.2Cl.sub.2/cyclohexane) (2.06 g, 67%). .sup.1H NMR (300 MHz) δ 5.98 (s, 4H, H.sub.3), 5.96-5.87 (m, 4H, H.sub.b), 5.26-5.16 (m, 8H, H.sub.c), 3.91 (d, .sup.3J.sub.a-b=5.4 Hz, 8H, H.sub.a), 3.85 (s, 2H, CH.sub.2), 3.72 (s, 12H, OCH.sub.3). .sup.13C NMR (75 MHz) δ 159.4 (C.sub.2), 148.0 (C.sub.4), 134.9 (C.sub.b), 116.0 (C.sub.c), 109.3 (C.sub.1), 91.3 (C.sub.3), 56.2 (OCH.sub.3), 53.4 (C.sub.a), 16.5 (CH.sub.2). HRMS: m/z: calcd for C.sub.29H.sub.39N.sub.2O.sub.4: 479.2904 [M+H].sup.+; found: 479.2891 [M+H].sup.+.

[0458] Compound 12 Precursor (Procedure Abis):

##STR00072##

[0459] The method 1 was applied to N,N-diallyl-3,5-dimethylaniline [Saitoh2004] (5.00 g, 24.84 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 10-50% CH.sub.2Cl.sub.2/cyclohexane) (3.25 g, 63%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 6.37 (s, 4H, H.sub.3), 5.94-5.81 (m, 4H, H.sub.b), 5.22-5.13 (m, 8H, H.sub.c), 3.92-3.85 (m, 10H, H.sub.a+CH.sub.2), 2.10 (s, 12H, CH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 146.6 (C.sub.4), 137.6 (C.sub.2), 134.7 (C.sub.b), 126.9 (C.sub.1), 116.0 (C.sub.3), 113.2 (C.sub.c), 52.7 (C.sub.a), 30.0 (CH.sub.2), 21.6 (CH.sub.3). HRMS: m/z: calcd for C.sub.29H.sub.39N.sub.2: 415.3108 [M+H].sup.+; found: 415.3124 [M+H].sup.+.

[0460] Compound 33 Precursor-1 (Procedure Abis):

##STR00073##

[0461] To a suspension of K.sub.2CO.sub.3 (6.0 g, 43.5 mmol) in dry MeCN (50 mL) was added 3,5-dimethoxyaniline (1.0 g, 6.53 mmol) under argon, and the reaction mixture was stirred for 2 h at room temperature. After eicosyl bromide (9.44 g, 26.11 mmol) was added, the mixture was refluxed for 24 h under stirring. Another portion of K.sub.2CO.sub.3 (6.0 g, 43.5 mmol) and eicosyl bromide (9.44 g, 26.11 mmol) were then added and the mixture was refluxed under stirring for another 24 h. The reaction mixture was then allowed to cool to room temperature and poured into a saturated NaCl solution. The resulting aqueous layer was extracted three times with methylene chloride. The organic layers were washed with distilled water, combined, dried over MgSO.sub.4 and filtered before removal of the solvent under reduced pressure. The crude mixture was purified via the Biotage Isolera One (silica-packed snap cartridge; 10-40% CH.sub.2Cl.sub.2/petroleum ether) to afford the expected product as a white solid (1.72 g, 37%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.83 (br s, 3H, H.sub.1+H.sub.3), 3.77 (s, 6H, OCH.sub.3), 3.23-3.18 (m, 4H, H.sub.a), 1.30-1.25 (m, 72H, H.sub.b-s), 0.90-0.86 (m, 6H, H.sub.t). .sup.3C NMR (100 MHz, CDCl.sub.3) δ 161.8 (C.sub.2), 150.1 (C.sub.4), 91.3 (C.sub.3), 87.3 (C.sub.1), 55.2 (OCH.sub.3), 51.4 (C.sub.a), 32.1 (C.sub.b), 29.9, 29.7, 29.5 (C.sub.c-p), 27.5 (C.sub.q), 27.3 (C.sub.r), 22.8 (C.sub.s), 14.3 (C.sub.r).

[0462] Compound 33 Precursor-2 (Procedure Abis):

##STR00074##

[0463] The method 1 was applied to 3,5-dimethoxy-N,N-dieicosylaniline (1.60 g, 2.24 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 50-100% CH.sub.2Cl.sub.2/petroleum ether) to afford a white microcrystalline solid (0.70 g, 44%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 5.84 (s, 4H, H.sub.3), 3.78 (s, 2H, CH.sub.2), 3.69 (s, 12H, OCH.sub.3), 3.18 (t, .sup.3J.sub.a-b=7.4 Hz, 8H, H.sub.a), 1.30-1.25 (m, 144H, H.sub.bs), 0.88 (t, .sup.3J.sub.t-s=6.8 Hz, 12H, H). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 160.0 (C.sub.2), 148.0 (C.sub.4), 109.7 (C.sub.1), 92.1 (C.sub.3), 56.5 (OCH.sub.3), 51.8 (C.sub.a), 32.1 (C.sub.b), 29.9, 29.7, 29.5 (C.sub.c-p), 27.8 (C.sub.q), 27.5 (C.sub.r), 22.8 (C.sub.s), 16.8 (CH.sub.2), 14.1 (C.sub.t).

[0464] Compound 34 Precursor-1 (Procedure Abis):

##STR00075##

[0465] To a suspension of K.sub.2CO.sub.3 (13.50 g, 89.87 mmol) and NaI (0.621 g, 4.14 mmol) in DMF (55 mL) was added under argon 3,5-dimethylaniline (4.00 mL, 32.08 mmol), and 2-chloroethyl methyl ether (6.40 mL, 70.40 mmol). The mixture was heated at 90° C. for 48 h under stirring. The reaction mixture was then allowed to cool to room temperature, filtered through a pad of celite and concentrated under reduced pressure. The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-5% EtOAc/cyclohexane) to afford the expected product (4.215 g, 55.3%). .sup.1H NMR (300 MHz, CDCl.sub.3) δ 6.40-6.35 (m, 3H, H.sub.1,3), 3.57-3.53 (m, 8H, H.sub.a,b), 3.37 (s, 6H, OCH.sub.3), 2.28 (s, 6H, CH.sub.3). .sup.13C NMR (75 MHz, CDCl.sub.3) δ 145.3 (C.sub.4), 138.5 (C.sub.2), 118.3 (C.sub.1), 110.3 (C.sub.3), 70.2 (OCH.sub.2), 59.1 (OCH.sub.3), 50.9 (NCH.sub.2), 21.8 (CH.sub.3).

[0466] Compound 34 Precursor-2 (Procedure Abis):

##STR00076##

[0467] The method 1 was applied to 3,5-dimethyl-N,N-bis(2-methoxyethyl)aniline (4.215 g, 17.76 mmol). The title compound was purified via the Biotage Isolera One (silica-packed snap cartridge; 0-30% CH.sub.2Cl.sub.2/cyclohexane) (2.58 g, 60%). .sup.1H NMR (300 MHz, CDCl.sub.3) δ 6.38 (s, 4H, H.sub.3), 3.91 (s, 2H, CH.sub.2), 3.57-3.54 (m, 16H, H.sub.a,b), 3.39 (s, 12H, OCH.sub.3), 2.13 (s, 12H, CH.sub.3). .sup.13C NMR (75 MHz, CDCl.sub.3) δ 145.5 (C.sub.4), 137.7 (C.sub.2), 126.7 (C.sub.1), 112.5 (C.sub.3), 70.3 (OCH.sub.2), 59.0 (OCH.sub.3), 50.9 (NCH.sub.2), 29.8 (CH.sub.2), 21.5 (CH.sub.3).

[0468] Compound 35-precursor:

##STR00077##

[0469] To a suspension of K.sub.2CO.sub.3 (20.88 g, 150.0 mmol) in DMF (100 mL) was added under argon methyl 3,4,5-trihydroxybenzoate (4.0 g, 21.6 mmol), and 1-bromooctane (11.28 mL, 72.24 mmol). The mixture was heated at 80° C. for 48 h under stirring. The reaction mixture was then allowed to cool to room temperature, before pouring into a large amount of water. The resulting mixture was then extracted with dietyl ether. The organic layers were washed with distilled water, combined, dried over MgSO.sub.4 and filtered before removal of the solvent under reduced pressure. The expected product was obtained as a white solid (7.35 g, 65.5%). .sup.1H NMR (400 MHz, CD.sub.3CN) δ 7.23 (s, 2H, H.sub.2′), 4.00-3.94 (m, 6H, H.sub.a′), 3.83 (s, 3H, OCH.sub.3), 1.78-1.72 (m, 6H, H.sub.b′), 1.36-1.23 (m, 24H, H.sub.c′-g′), 0.90-0.86 (s, 9H, H.sub.h′). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 167.1 (CO.sub.2Me), 152.9 (C.sub.3′), 142.5 (C.sub.4′), 124.8 (C.sub.1′), 108.1 (C.sub.2′), 69.3 (C.sub.a′), 52.2 (OCH.sub.3), 32.0, 30.5, 29.6, 29.4, 26.2, 22.8, 14.2 (C.sub.h′).

Method 2: General Procedure for Synthesis of Target Diarylmethyliums

[0470] 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 a 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.2C.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.−.

[0471] Compound 1-DDQH.sup.− (Procedure Abis):

##STR00078##

[0472] The method 2 was applied to 4,4′-methylenebis(3,5-dimethoxy-N,N-dioctylaniline) (2.94 g, 3.83 mmol). The title compound was purified by a simple washing with cyclohexane and CH.sub.2Cl.sub.2 to yield the desired carbenium as a metal-like lacquer, displaying either a magenta or a copper/gold luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (3.4 g, 89.3%). .sup.1H NMR (400 MHz, CD.sub.3CN) δ 8.29 (s, 1H, CH.sup.+), 5.85 (s, 4H, H.sub.3), 3.82 (s, 12H, OCH.sub.3), 3.56-3.49 (m, 8H, H.sub.a), 1.74-1.64 (m, 8H, H), 1.45-1.22 (m, 40H, H.sub.c-g), 0.94-0.83 (m, 12H, H.sub.h). .sup.13C NMR (100 MHz, CD.sub.3CN) δ 165.1 (C.sub.2), 158.7 (C.sub.4), 142.5 (CH.sup.+), 112.0 (C.sub.1), 89.4 (C.sub.3), 56.9 (OCH.sub.3), 52.5 (C.sub.a), 32.5 (C), 30.0 (C), 28.4 (C.sub.d), 27.5 (Ce), 27.5 (C.sub.f), 23.4 (C.sub.g), 14.4 (C.sub.h). HRMS (ESI+): m/z: calcd for C.sub.49H.sub.85N.sub.2O.sub.4: 765.6504 [M−DDQH].sup.+; found: 765.6505 [M−DDQH].sup.+. HRMS (ESI−): m/z: calcd for C.sub.8HCl.sub.2N.sub.2O.sub.2: 226.9421 [DDQH].sup.−; found: 226.9423 [DDQH].sup.−.

[0473] Compound 1-PF.sub.6.sup.− (Procedure Abis):

##STR00079##

[0474] A small quantity of the previously described bis(4-(dioctylamino)-2,6-dimethoxyphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (0.463 g, 0.46 mmol) was engaged in a metathesis step using potassium hexafluorophosphate. It's worth noticing that while dropwise addition of the acetonitrile concentrated solution of 1-DDQH.sup.− into the saturated aqueous solution of KPF.sub.6, a highly reflective magenta-colored film self-assembled at the air-liquid interface (as can be seen in FIG. 2). The film was harvested, taken up in CH.sub.2Cl.sub.2 and washed with a minimum amount of distilled water to yield the desired carbenium as a metal-like lacquer, displaying either a magenta or a copper/gold luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (0.356 g, 85.0%). .sup.1H NMR (400 MHz, CD.sub.3CN) δ 8.29 (s, 1H, CH.sup.+), 5.85 (s, 4H, H.sub.3), 3.82 (s, 12H, OCH.sub.3), 3.56-3.49 (m, 8H, H.sub.a), 1.74-1.64 (m, 8H, H), 1.44-1.26 (m, 40H, H.sub.eg), 0.95-0.88 (m, 12H, H.sub.h). .sup.13C NMR (100 MHz, CD.sub.3CN) δ 165.1 (C.sub.2), 158.8 (C.sub.4), 142.5 (CH.sup.+), 111.9 (C.sub.1), 89.5 (C.sub.3), 56.8 (OCH.sub.3), 52.4 (C.sub.a), 32.5 (C.sub.b), 30.0 (C.sub.c), 28.3 (C.sub.a), 27.6 (C.sub.e), 27.5 (C.sub.f), 23.4 (C.sub.g), 14.4 (C.sub.h). HRMS (ESI+): m/z: calcd for C.sub.49H.sub.85N.sub.2O.sub.4: 765.6504 [M−PF.sub.6].sup.+; found: 765.6505 [M−PF.sub.6].sup.+. HRMS (ESI−): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.−; found: 144.9650 [PF.sub.6].sup.−.

[0475] Compound 5-DDQH.sup.− (Procedure Abis):

##STR00080##

[0476] The method 2 was applied to 4,4′-methylenebis(N,N-bis(2-methoxyethyl)-3,5-dimethoxy-aniline) (0.934 g, 1.69 mmol). The title compound was purified by simple washing with Et.sub.2O and CH.sub.2C.sub.2 to yield the desired carbenium as a reddish copper metallic solid (1.2 g, 91.3%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.34 (s, 1H, CH.sup.+), 6.02 (s, 4H, H.sub.3), 3.83 (s, 12H, .sup.2OCH.sub.3), 3.81 (t, 8H, NCH.sub.2), 3.65 (t, 8H, OCH.sub.2), 3.33 (s, 12H, OCH.sub.3).sup.13C NMR (75 MHz, CD.sub.3CN) δ 165.1 (C.sub.2), 160.1 (C.sub.4), 143.3 (CH.sup.+), 112.4 (C.sub.1), 90.3 (C.sub.3), 71.1 (OCH.sub.2), 59.3 (OCH.sub.3), 57.0 (.sup.2OCH.sub.3), 52.6 (NCH.sub.2). HRMS (ESI+): m/z: calcd for C.sub.29H.sub.45N.sub.2O.sub.8: 549.3170 [M−DDQH].sup.+; found: 549.3168 [M−DDQH].sup.+. HRMS (ESI−): m/z: calcd for C.sub.8HCl.sub.2N.sub.2O.sub.2: 226.9421 [DDQH].sup.−; found: 227.2017 [DDQH].sup.−.

[0477] Compound 5-PF.sub.6.sup.−(Procedure Abis):

##STR00081##

[0478] A small quantity of the previously described bis(4-(bis(2-methoxyethyl)amino)-2,6-dimethoxyphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (0.616 g, 0.79 mmol) was engaged in a metathesis step using potassium hexafluorophosphate. It's worth noticing that while dropwise addition of the acetonitrile concentrated solution of 5-DDQH.sup.− into the saturated aqueous solution of KPF.sub.6, a highly reflective gold-colored film self-assembled at the air-liquid interface (as can be seen in FIG. 7). The film was harvested, taken up in CH.sub.2Cl.sub.2 and washed with a minimum amount of distilled water. to yield the desired carbenium as a metal-like lacquer, displaying either a copper/gold or a green luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (0.465 g, 84.7%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.34 (s, 1H, CH.sup.+), 6.02 (s, 4H, H.sub.3), 3.83 (s, 12H, .sup.2OCH.sub.3), 3.81 (t, 8H, NCH.sub.2), 3.65 (t, 8H, OCH.sub.2), 3.33 (s, 12H, OCH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 165.1 (C.sub.2), 160.2 (C.sub.4), 143.3 (CH.sup.+), 112.4 (C.sub.1), 90.3 (C.sub.3), 71.1 (OCH.sub.2), 59.3 (.sup.bOCH.sub.3), 57.0 (.sup.2OCH.sub.3), 52.6 (NCH.sub.2). HRMS (ESI+): m/z: calcd for C.sub.29H.sub.45N.sub.2O.sub.8: 549.3170 [M−PF.sub.6].sup.+; found: 549.3167 [M−PF.sub.6].sup.+. HRMS (ESI−): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.−; found: 144.9650 [PF.sub.6].sup.−. UV-vis-NIR (CH.sub.3CN) λmax/nm (ε/L mol.sup.−1 cm.sup.−1): 588 (87 178) (as can be seen in FIG. 1).

[0479] Compound 11-DDQH.sup.− (Procedure Abis):

##STR00082##

[0480] The method 2 was applied to 4,4′-methylenebis(N,N-diallyl-3,5-dimethoxyaniline) (3.67 g, 7.67 mmol) to yield the title compound that was simply filtered from the reaction mixture as a microcrystallized lustrous green solid (affording a blue solution) (4.92 g, 91%). .sup.1H NMR (300 MHz, DMSO-d.sub.6) δ 8.24 (s, 1H, CH.sup.+), 6.08-5.81 (m, 8H, H.sub.b+H.sub.3), 5.38-5.14 (m, 8H, H.sub.c), 4.40-4.15 (m, 8H, H.sub.a), 3.81 (s, 12H, OCH.sub.3). .sup.13C NMR (75 MHz, DMSO-d.sub.6) δ 163.6 (C.sub.2), 158.3 (C.sub.4), 141.5 (CH.sup.+), 132.5 (C.sub.b), 117.5 (C.sub.c), 110.9 (C.sub.1), 89.1 (C.sub.3), 56.3 (OCH.sub.3), 53.4 (C.sub.a).

[0481] Compound 11-PF.sub.6.sup.− (Procedure Abis):

##STR00083##

[0482] A small quantity of the previously described bis(4-(diallylamino)-2,6-dimethoxyphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (1.0 g, 1.42 mmol) was engaged in a metathesis step using potassium hexafluorophosphate to give after evaporation a metal-like lacquer, displaying either a copper or a green luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (as can be seen in FIGS. 13 & 14) (0.75 g, 88%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.36 (s, 1H, CH.sup.+), 5.99-5.90 (m, 4H, H.sub.b), 5.89 (s, 4H, H.sub.3), 5.31-5.20 (m, 8H, H.sub.c), 4.23-4.15 (d, .sup.3J.sub.a-b=5.1 Hz, 8H, H.sub.a), 3.79 (s, 12H, OCH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 165.2 (C.sub.2), 160.0 (C.sub.4), 143.9 (CH.sup.+), 133.0 (C.sub.b), 118.0 (C.sub.c), 112.5 (C.sub.1), 90.0 (C.sub.3), 57.0 (OCH.sub.3), 54.6 (C.sub.a). HRMS (ESI+): m/z: calcd for C.sub.29H.sub.37N.sub.2O.sub.4: 477.2748 [M−PF.sub.6].sup.+; found: 477.2767 [M−PF.sub.6].sup.+. HRMS (ESI−): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.−; found: 145.0754 [PF.sub.6].sup.−. UV-vis-NIR (CH.sub.3CN) λmax/nm (ε/L mol.sup.−1 cm.sup.−1): 585.5 (62 616) (as can be seen in FIG. 1).

[0483] Compound 12-PF.sub.6.sup.−(Procedure Abis):

##STR00084##

[0484] The method 2 was applied to 4,4′-methylenebis(N,N-diallyl-3,5-dimethylaniline) (1.74 g, 4.21 mmol). The crude product was washed with EtOAc to give after evaporation the title compound as a metal-like lacquer, displaying either a magenta or a bronze luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (as can be seen in FIGS. 17 & 18) (1.60 g, 68%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.45 (s, 1H, CH.sup.+), 6.66 (s, 4H, H.sub.3), 5.98-5.89 (m, 4H, H.sub.b), 5.30-5.20 (m, 8H, H.sub.c), 3.92-3.85 (d, .sup.3J.sub.a-b=5.1 Hz, 8H, H.sub.a), 2.22 (s, 12H, CH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 159.3 (CH.sup.+), 157.1 (C.sub.4), 148.6 (C.sub.2), 132.7 (C.sub.b), 130.6 (C), 118.0 (C), 115.5 (C.sub.3), 54.2 (C.sub.a), 21.9 (CH.sub.3). HRMS (ESI+): m/z: calcd for C.sub.29H.sub.37N.sub.2: 413.2951 [M−PF.sub.6].sup.+; found: 413.2949 [M−PF.sub.6].sup.+; calcd for C.sub.30H.sub.41N.sub.2O: 445.3213 [M-PF.sub.6+MeOH].sup.+; found: 445.3225 [M−PF.sub.6+MeOH].sup.+. HRMS (ESI−): m/z: calcd for F.sub.6P: 144.9647 [PF.sub.6].sup.−; found: 145.0840 [PF.sub.6].sup.−. UV-vis-NIR (CH.sub.3CN) λmax/nm (ε/L mol.sup.−1 cm.sup.−1): 650 (70 133) (as can be seen in FIG. 1).

[0485] Compound 33-PF.sub.6.sup.− (Procedure Abis):

##STR00085##

[0486] The method 2 was applied to 4,4′-methylenebis(3,5-dimethoxy-N,N-dieicosylaniline) (0.70 g, 0.486 mmol). The crude product was washed with diethyl ether to give after evaporation the title compound as a metal-like lacquer. (0.70 g, 91%). .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.34 (s, 1H, CH.sup.+), 5.76 (s, 4H, H.sub.3), 3.85 (s, 12H, OCH.sub.3), 3.49 (t, .sup.3J.sub.a-b=7.4 Hz, 8H, H.sub.a), 1.70 (m, 8H, H.sub.b), 1.40-1.25 (m, 136H, H.sub.e s), 0.88 (t, .sup.3J.sub.t-s=6.8 Hz, 12H, H.sub.t). .sup.13C NMR (100 MHz, CDCl.sub.3) δ 164.8 (C.sub.2), 158.3 (C.sub.4), 143.4 (CH.sup.+), 112.4 (C.sub.1), 88.9 (C.sub.3), 56.2 (OCH.sub.3), 52.3 (C.sub.a), 32.1 (C.sub.b), 29.9, 29.7, 29.5 (C.sub.c-p), 28.2 (C.sub.q), 27.3 (C.sub.r), 22.8 (C.sub.s), 14.1 (C.sub.t).

[0487] Compound 34-DDQH.sup.− (Procedure Abis):

##STR00086##

[0488] The method 2 was applied to 4,4′-methylenebis(N,N-bis(2-methoxyethyl)-3,5-dimethylaniline) (1.52 g, 3.12 mmol). The title compound was purified by a simple washing with diethyl ether to yield the desired carbenium as a metal-like pale pink lacquer (1.83 g, 82.0%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.37 (s, 1H, CH.sup.+), 6.71 (s, 4H, H.sub.3), 3.79 (t, .sup.3J.sub.a-b=5.3 Hz, 8H, NCH.sub.2), 3.61 (t, .sup.3J.sub.a-b=5.3 Hz, 8H, OCH.sub.2), 3.30 (s, 12H, OCH.sub.3), 2.21 (s, 12H, CH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 158.3 (CH.sup.+), 157.0, 157.5 (C.sub.4), 153.2, 148.2 (C.sub.2), 130.8, 130.4 (C.sub.1), 118.3, 115.5 (C.sub.3), 101.4, 70.8 (OCH.sub.2), 59.3 (OCH.sub.3), 52.4 (NCH.sub.2), 22.0 (CH.sub.3).

[0489] Compound 34-PF.sub.6.sup.− (Procedure Abis):

##STR00087##

[0490] A small quantity of the previously described bis(4-(bis(2-methoxyethyl)amino)-2,6-dimethylphenyl)methylium 2,3-dichloro-5,6-dicyano-4-hydroxyphenolate (0.300 g, 0.42 mmol) was engaged in a metathesis step using potassium hexafluorophosphate. It's worth noticing that while dropwise addition of the acetonitrile concentrated solution of 34-DDQH.sup.− into the saturated aqueous solution of KPF.sub.6, a highly reflective magenta-colored film self-assembled at the air-liquid interface (as can be seen in FIG. 21). The film was harvested, taken up in CH.sub.2Cl.sub.2 and washed with a minimum amount of distilled water to yield the desired carbenium as a metal-like lacquer, displaying either a copper or a magenta/blue luster whether the round-bottom flask in which evaporation occurred was observed from the outside or not (0.260 g, 98%). .sup.1H NMR (300 MHz, CD.sub.3CN) δ 8.40 (s, 1H, CH.sup.+), 6.73 (s, 4H, H.sub.3), 3.80 (t, .sup.3J.sub.a-b=5.5 Hz, 8H, NCH.sub.2), 3.62 (t, .sup.3J.sub.a-b=5.5 Hz, 8H, OCH.sub.2), 3.31 (s, 12H, OCH.sub.3), 2.23 (s, 12H, CH.sub.3). .sup.13C NMR (75 MHz, CD.sub.3CN) δ 158.3 (CH.sup.+), 157.5 (C.sub.4), 148.2 (C.sub.2), 130.4 (C.sub.1), 115.5 (C.sub.3), 70.8 (OCH.sub.2), 59.3 (OCH.sub.3), 52.3 (NCH.sub.2), 21.9 (CH.sub.3).

[0491] Compound 35-PF.sub.6— (procedure Gbis):

##STR00088##

[0492] To a flask charged with TMEDA (0.12 mL, 0.80 mmol) and anhydrous THF (2.5 mL) cooled at −78° C. under argon was added n-butyllithium in hexane solution (4.6 mL, 11.5 mmol). The milky solution was stirred for 15 min, before dropwise addition of a THF solution of 3,5-dimethoxy-N,N-bis(2-methoxyethyl)aniline (2.15 g, 8.0 mmol). The vigorously stirred mixture was maintained at −78° C. for another 15 min and then allowed to gradually warm to room temperature. After 3 h, the mixture was then cooled again at −78° C. and diluted with 6 mL of anhydrous THF before addition of methyl 3,4,5-tris(octyloxy)benzoate (2.08 g, 4.0 mmol). The reaction mixture temperature was then maintained at −78° C. for another 15 min and stirred at room temperature for 36 h. To the reaction mixture was added H.sub.2O (20 mL). The solvent was removed and the residue was taken up in a minimum amount of methanol before addition of a 60% aqueous HPF.sub.6 solution (4.0 mmol). The product was extracted with dichloromethane and the solvent volume was reduced under vacuum. The resulting highly lustrous residue was washed several times with diethyl ether to give the expected compound, which was further purified by recrystallization. [0493] References reporting the preparation and characterization of some starting materials used in the above described general: [0494] [Yang1999]: Yang, S.-C., Hung, C.-W. Synthesis, 1999, 10, 1747-1752. [0495] [Saitoh2004] Saitoh, T., Yoshida, S., Ichikawa, J. Org. Lett., 2004, 6, 4563-4565.

II—Optical Properties of the Compounds According to the Invention

II—1. Absorption Properties

[0496] Measurement of the molar extinction coefficients of compounds 5-PF.sub.6.sup.−, 11-PF.sub.6.sup.−, 12-PF.sub.6.sup.− was carried as follows: for each compound, three independent 10-5 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).

[0497] As it appears on FIG. 1, 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).

[0498] Accordingly, chromophoric properties of compounds of the invention are directly observed from these solutions. For example, an intense deep blue color is observed for 5-PF.sub.6.sup.−, 11-PF.sub.6.sup.−, 12-PF.sub.6.sup.− dissolved in acetonitrile.

II-2. Other Optical Properties

[0499] FIG. 2 corresponds to a picture of a magenta-colored liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 1-DDQH.sup.−, into a stirred saturated aqueous solution of KPF.sub.6. The impressive reflective properties of the film are maintained whether the solution is stirred or not. This feature is of peculiar interest to design liquid mirrors, specifically for astronomy purposes, needing a parabolic surface, usually shaped by rotation.

[0500] FIG. 3 corresponds to a picture of a magenta-colored mirror of compound 1-PF.sub.6.sup.− that forms on the glass wall of a container, resulting from evaporation of a concentrated acetonitrile solution of chromophoric compound 1-PF.sub.6.sup.−. This self-assembled organic material constitutes a real mirror that reflects with fidelity surrounding objects.

[0501] FIG. 4 represents a photograph of a magenta reflective film covering a PTFE magnetic stir bar and its retriever after dipping into the solution displaying at the air-liquid interface the liquid mirror illustrated in FIG. 2, thus demonstrating the ability of the film to be transferred from the top of a fluid onto other surfaces, while keeping its reflective features.

[0502] FIG. 5 represents a macroscopic view of compound 5-DDQH.sup.− in its solid form, characterized by its reddish copper flakes appearance, demonstrating the angle-dependency of the reflective properties.

[0503] FIG. 6 represents a microscopic view of compound 5-DDQH.sup.− in its solid form, characterized by its metallic and copper/gold flakes appearance, obtained with a Zeiss-Stemi 2000-C microscope, demonstrating impressive reflective properties (metal foil aspect).

[0504] FIG. 7 corresponds to a picture of a gold-like liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 5-DDQH.sup.− into a stirred saturated aqueous solution of KPF.sub.6. The impressive reflective properties of the film are maintained whether the solution is stirred or not. This feature is of peculiar interest to design liquid mirrors, specifically for astronomy purposes, needing a parabolic surface, usually shaped by rotation.

[0505] FIG. 8 corresponds to a picture of a self-assembled gold-like liquid mirror observed few minutes after dropwise addition of an acetonitrile solution of compound 5-PF.sub.6.sup.− onto the surface of a saturated aqueous solution of NaCl. This homogeneous low-dimensional organic material constitutes a real mirror that reflects with fidelity surrounding objects.

[0506] FIG. 9 corresponds to a picture of a copper/gold-like mirror of compound 5-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 5-PF.sub.6.sup.−. This self-assembled organic material constitutes a real mirror that reflects with fidelity surrounding objects.

[0507] FIG. 10 represents a macroscopic view of compound 5-PF.sub.6.sup.− in its polycrystalline form, characterized by its green metallic luster appearance, demonstrating the angle-dependency of the reflective properties.

[0508] FIG. 11 represents a microscopic view of compound 5-PF.sub.6.sup.− in its polycristalline form, obtained with a Zeiss-Stemi 2000-C microscope, demonstrating the angle-dependency of the reflective properties.

[0509] FIG. 12 displays a microscopic view of compound 11-PF.sub.6.sup.− in its microcrystallized form, characterized by its impressive dual metallic (copper/gold & bronze/green) reflective properties, obtained with a Zeiss-Stemi 2000-C microscope.

[0510] FIG. 13 represents a photograph of the copper/gold reflective mirror formed on the inner-wall of a round-bottom flask after simple evaporation of a concentrated solution of 11-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).

[0511] FIG. 14 represents a photograph (outside view) of the green-bronze reflective mirror formed on the inner-wall of a round-bottom flask after simple evaporation of a concentrated solution of 11-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).

[0512] FIG. 15 displays a microscopic view of compound 11-DDQH.sup.− in its microcrystallized form, characterized by its glittering appearance, obtained with a Zeiss-Stemi 2000-C microscope.

[0513] FIG. 16 displays a macroscopic view of compound 12-PF.sub.6.sup.− in its solid form, characterized by its dual magenta/copper luster appearance, in accordance with the dual metallic appearance illustrated in following FIGS. 17 & 18.

[0514] FIG. 17 represents a photograph of a magenta reflective mirror of compound 12-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask after simple evaporation of a concentrated acetonitrile solution of 12-PF.sub.6.sup.−, 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).

[0515] FIG. 18 represents a photograph of the outside view of a copper reflective mirror of compound 12-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask after simple evaporation of a concentrated acetonitrile solution of 12-PF.sub.6.sup.−, 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).

[0516] FIG. 19 corresponds to a picture of a purple liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 33-DDQH.sup.− into a stirred saturated aqueous solution of KPF.sub.6. The impressive reflective properties of the film are maintained whether the solution is stirred or not. This feature is of peculiar interest to design liquid mirrors.

[0517] FIG. 20 represents a macroscopic view of compound 34-DDQH.sup.− in form of a metallic pink lacquer, demonstrating the angle-dependency of the reflective properties.

[0518] FIG. 21 corresponds to a picture of a magenta/pink-like liquid mirror obtained by dropwise addition of an acetonitrile solution of compound 34-DDQH.sup.− into a stirred saturated aqueous solution of KPF.sub.6. The impressive reflective properties of the film are maintained whether the solution is stirred or not. This feature is of peculiar interest to design liquid mirrors.

[0519] FIG. 22 represents a photograph of a magenta/pink reflective film covering a PTFE magnetic stir bar and its retriever after dipping into the solution displaying at the air-liquid interface the liquid mirror illustrated in FIG. 21, thus demonstrating the ability of the film to be transferred from the top of a fluid onto other surfaces, while keeping its reflective features.

[0520] FIG. 23 displays a macroscopic view of compound 34-PF.sub.6.sup.− in its solid form, characterized by its reddish copper luster appearance, demonstrating the angle-dependency of the reflective properties.

[0521] FIG. 24 represents a photograph of a magenta/blue-like mirror of compound 34-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask after simple evaporation of a concentrated acetonitrile solution of 34-PF.sub.6.sup.−, 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).

[0522] FIG. 25 represents a photograph of the outside view of a copper reflective mirror of compound 34-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask after simple evaporation of a concentrated acetonitrile solution of 34-PF.sub.6.sup.−, hence showing the propensity of the molecule to self-assemble to yield a well-shaped coating that displays optical properties of interest (i.e. obtaining of a reflective metal-like luster).

[0523] FIG. 26 represents a photograph of a reflective layer of compound 35-PF.sub.6.sup.− that forms on the inner-wall of a round-bottom flask after simple evaporation of a concentrated dichloromethane solution of 35-PF.sub.6.sup.−, 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).

III—Films Made of Compounds According to the Invention

III-1. Elaboration and Characterization of Solid Films Made of Compounds of the Invention: Spin Coating and Quantitative Reflectance Measurements

[0524] 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 5 mg/mL) can be prepared.

[0525] This solution is spin-coated onto a substrate, and after solvent evaporation under ambient conditions, a uniform film exhibiting a reflective appearance is obtained.

[0526] It has been observed that films obtained with compounds according to the invention are able to cover various surfaces, notably glass (see FIGS. 3, 9, 13 & 14, 17 & 18, 24 & 25, 26).

[0527] Films of different thicknesses can be spin-coated by varying the spin-coating speed or acceleration or duration, or by varying the concentration or 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.

[0528] Drop-casting, dip-coating, bar-coating, spraying and doctor blade techniques may also represent alternative efficient modes of preparation of solid films made of compounds of the invention. Optical properties are somewhat angle-dependent and reinforced by the background color of the substrate.

III-2. Elaboration and Characterization of Organic Metal-Like Liquid Films Made of Compounds of the Invention: Dropwise Addition and Quantitative Reflectance Measurements

[0529] Whether the compound of interest bears rather hydrophilic or lipophilic moieties, it is mandatory to appropriately choose the nature of the deposition fluid in order to obtain a film with optimized optical properties.

[0530] A solution of one of the compounds (around 10 mg/mL or more) is dropwise added into a stirred saturated aqueous solution (of KPF.sub.6 or NaCl for example). After 30 min-1 h, a homogeneous reflective film covers the liquid surface, that can if needed be carefully transferred onto another surface. In condition that the compound is deposited on an appropriate liquid (regarding its physicochemical properties), such films can be stored at least weeks without visible degradation of their optical properties.

[0531] It has been observed that films obtained with compounds according to the invention are able to cover various surfaces (notably glass and PTFE). More precisely, compounds 1-PF.sub.6.sup.−, 5-PF.sub.6.sup.− and 34-PF.sub.6.sup.− are particularly prone to deposit on PTFE-coated objects (see FIGS. 4 & 22) which are usually known for their anti-stick properties, what can open new fields of application.

[0532] Spraying or more sophisticated techniques may be envisioned to perform an efficient mode of preparation of films made of compounds of the invention (regarding the purpose or the type of liquid on which deposit).