Polymers and compounds based on dipyrrolo[1,2-B:1',2'-G][2,6]naphthyridine-5,11-dione

Abstract

Polymers containing a repeating unit of the formula [ArYAr] (V), and compounds of formula R.sup.10ArYArR.sup.10 (I), where Y is a group of formula ##STR00001##
and organic devices containing the polymers. The polymers and compounds have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds are used in organic field effect transistors, organic photovoltaics and photodiodes.

Claims

1. A compound of formula
R.sup.10ArYArR.sup.10(I), wherein Ar is a group of formula [Ar.sup.3].sub.c[Ar.sup.2].sub.b[Ar.sup.1].sub.a**, Ar is a group of formula **[Ar.sup.1].sub.a[Ar.sup.2].sub.b[Ar.sup.3].sub.c, Y is a group of formula ##STR00122## wherein ** indicates the bonding to Y, a is 0, 1, 2, or 3, a is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c is 0, 1, 2, or 3; m1 is 0, 1, or 2; m2 is 0, 1, or 2; U.sup.1 is O, or S; U.sup.2 is O, or S; T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are independently of each other: a hydrogen, halogen, cyano, COOR.sup.103, OCOR.sup.103, NR.sup.112COR.sup.103, CONR.sup.112R.sup.113, OR.sup.103, SR.sup.103, SOR.sup.103, SO.sub.2R.sup.103, NR.sup.112SO.sub.2R.sup.103, NR.sup.112R.sup.113, NO.sub.2, C.sub.7-C.sub.25arylalkyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy; a C.sub.1-C.sub.100alkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.2-C.sub.100alkenyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.2-C.sub.100alkinyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.3-C.sub.12cycloalkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.6-C.sub.24aryl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; a C.sub.2-C.sub.20heteroaryl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; a COC.sub.1-C.sub.18alkyl group, a COC.sub.5-C.sub.12cycloalkyl group, or COOC.sub.1-C.sub.18alkyl group; Ar.sup.1 and Ar.sup.1 are independently of each other ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## Ar.sup.2, Ar.sup.2, Ar.sup.3 and Ar.sup.3 have independently of each other the meaning of Ar.sup.1, or are independently of each other ##STR00128## ##STR00129## wherein X is O, S, Se, Te, or NR.sup.8, X is O, or S, X.sup.1, X.sup.2 and X.sup.3 are independently of each other S, O, NR.sup.107, Si(R.sup.117)(R.sup.117), Ge(R.sup.117)(R.sup.117), C(R.sup.108)(R.sup.109), C(O), C(CR.sup.110R.sup.111), ##STR00130## X.sup.4 and X.sup.4 are independently of each other S, O, NR.sup.107, Si(R.sup.117)(R.sup.117), Ge(R.sup.117)(R.sup.117), C(R.sup.108)(R.sup.109), C(O), C(CR.sup.110R.sup.111), R.sup.3 and R.sup.3 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.4, R.sup.4, R.sup.5, R.sup.5, R.sup.6, and R.sup.6 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.7, R.sup.7, R.sup.9 and R.sup.9 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C.sub.1-C.sub.25arylalkyl; R.sup.8 and R.sup.8 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy, or C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C.sub.7-C.sub.25arylalkyl; R.sup.10 and R.sup.10 are independently of each other hydrogen, halogen, NO.sub.2, NR.sup.112R.sup.113, cyano, C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25alkyl which is substituted one or more times by E and/or interrupted one or more times by D, ##STR00131## COOC.sub.1-C.sub.18alkyl, C.sub.4-C.sub.18cycloalkyl group, C.sub.4-C.sub.18cycloalkyl group, which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkylthio, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, C.sub.7-C.sub.25aralkyl, which is substituted by G, or a group of formulae IVa to IVk, ##STR00132## ##STR00133## wherein X.sup.5 is O, S, Se, Te, or NR.sup.59, R.sup.11 and R.sup.11 are independently of each other C.sub.1-C.sub.25alkyl group, C.sub.7-C.sub.25arylalkyl, or a phenyl group, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.5alkoxy; R.sup.12 and R.sup.12 are independently of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25alkoxy, C.sub.7-C.sub.25arylalkyl, or ##STR00134## R.sup.13 is a C.sub.1-C.sub.8alkyl group, or a tri(C.sub.1-C.sub.8alkyl)silyl group; R.sup.22 to R.sup.26 and R.sup.29 to R.sup.58 represent independently of each other H, halogen, cyano, NO.sub.2, NR.sup.112R.sup.113, C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, a C.sub.4-C.sub.18cycloalkyl group, a C.sub.4-C.sub.18cycloalkyl group, which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.25alkylthio, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25aralkyl, or C.sub.7-C.sub.25aralkyl, which is substituted by G, R.sup.27 and R.sup.28 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, halogen, cyano or C.sub.7-C.sub.25aralkyl, or R.sup.27 and R.sup.28 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms, R.sup.59 is hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.15aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C.sub.7-C.sub.25arylalkyl, R.sup.60 is hydrogen, C.sub.1-C.sub.18haloalkyl, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C.sub.1-C.sub.18alkanoyl, or C.sub.7-C.sub.25arylalkyl, R.sup.103 and R.sup.103 are independently of each other hydrogen, C.sub.1-C.sub.100alkyl, C.sub.1-C.sub.25alkyl substituted by E and/or interrupted with D, C.sub.2-C.sub.25alkenyl, C.sub.2-C.sub.25alkenyl substituted by E and/or interrupted with D, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G, R.sup.104 and R.sup.104 are independently of each other hydrogen, CN, C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.10aryl, which may optionally be substituted by G, or C.sub.2-C.sub.8heteroaryl, which may optionally be substituted by G, R.sup.105, R.sup.105, R.sup.106 and R.sup.106 are independently of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.18alkoxy, R.sup.107 is hydrogen, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18perfluoroalkyl; C.sub.1-C.sub.25alkyl, which may be interrupted by O, or S; or COOR.sup.103; R.sup.103 is as defined above; R.sup.108 and R.sup.109 are independently of each other H, C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25alkyl which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl, or R.sup.108 and R.sup.109 together form a group of formula CR.sup.110R.sup.111, wherein R.sup.110 and R.sup.111 are independently of each other H, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, or C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G, or R.sup.108 and R.sup.109 together form a five or six membered ring, which optionally can be substituted by C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl, wherein D is CO, COO, S, O, or NR.sup.112, E is C.sub.1-C.sub.8alkylthio, C.sub.1-C.sub.8alkoxy, CN, NR.sup.112R.sup.113, CONR.sup.112R.sup.113, or halogen, G is E, or C.sub.1-C.sub.18alkyl, and R.sup.112 and R.sup.113 are independently of each other H; C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.114 is C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, R.sup.115 and R.sup.115 are independently of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25alkoxy, C.sub.7-C.sub.25arylalkyl, or ##STR00135## R.sup.116 is a C.sub.1-C.sub.8alkyl group, or a tri(C.sub.1-C.sub.8alkyl)silyl group; R.sup.117 and R.sup.117 are independently of each other C.sub.1-C.sub.25alkyl group, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy; R.sup.118, R.sup.119, R.sup.120 and R.sup.121 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.122 and R.sup.122 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy, or C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, or C.sub.7-C.sub.25arylalkyl; and E.sub.Si is SiR.sup.161R.sup.162R.sup.163 or OSiR.sup.161R.sup.162R.sup.163, wherein R.sup.161, R.sup.162 and R.sup.163 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, C.sub.3-C.sub.12cycloalkyl which might optionally be substituted with C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.25haloalkyl, C.sub.2-C.sub.25alkenyl, OSiR.sup.164R.sup.165R.sup.166, (OSiR.sup.164R.sup.165).sub.dR.sup.166, C.sub.1-C.sub.25alkoxy, C.sub.3-C.sub.24(hetero)aryloxy, NR.sup.167R.sup.168, halogen, C.sub.1-C.sub.25acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C.sub.1-C.sub.24alkyl, halogen, cyano or C.sub.1-C.sub.25alkoxy; R.sup.164, R.sup.165 and R.sup.166 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, C.sub.3-C.sub.12cycloalkyl, which might optionally be substituted with C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.25haloalkyl, C.sub.2-C.sub.25alkenyl, OSiR.sup.169R.sup.170R.sup.171, (OSiR.sup.169R.sup.170).sub.dR.sup.171, C.sub.1-C.sub.25alkoxy, C.sub.3-C.sub.24(hetero)aryloxy, NR.sup.167R.sup.168, halogen, C.sub.1-C.sub.25acyloxy, phenyl, phenyl which is substituted 1 to 3 times by C.sub.1-C.sub.24alkyl, halogen, cyano or C.sub.1-C.sub.25alkoxy; R.sup.169, R.sup.170 and R.sup.171 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, C.sub.3-C.sub.12cycloalkyl, which might optionally be substituted with C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.25haloalkyl, C.sub.2-C.sub.25alkenyl, OSi(CH.sub.3).sub.3, C.sub.1-C.sub.25alkoxy, C.sub.3-C.sub.24(hetero)aryloxy, NR.sup.167R.sup.168, halogen, C.sub.1-C.sub.25acyloxy, phenyl, phenyl, which is substituted 1 to 3 times by C.sub.1-C.sub.24alkyl, halogen, cyano or C.sub.1-C.sub.25alkoxy; R.sup.167 and R.sup.168 are independently of each other hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25arylalkyl; d is an integer from 1 to 50; R.sup.214 and R.sup.215 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, CN or COOR.sup.216; and R.sup.216 is C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25haloalkyl, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.24aryl or C.sub.2-C.sub.20heteroaryl.

2. The compound according to claim 1, which is a compound of formula ##STR00136##

3. The compound according to claim 1, which is a compound of formula ##STR00137##

4. The compound according to claim 1, wherein U.sup.1 and U.sup.2 are O.

5. The compound according to claim 1, wherein T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are H, a C.sub.1-C.sub.38alkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, cyano, or E.sub.Si; and/or can optionally be interrupted by O, S, or NR.sup.60, wherein R.sup.60 is C.sub.1-C.sub.25alkyl, or phenylC.sub.1-C.sub.4alkyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy, wherein E.sub.Si is SiR.sup.161R.sup.162R.sup.163; R.sup.161, R.sup.162 and R.sup.163 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.6cycloalkyl, which might optionally be substituted with C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSiR.sup.164R.sup.165R.sup.166, (OSiR.sup.64R.sup.165).sub.dR.sup.166, or phenyl; R.sup.164, R.sup.165 and R.sup.166 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSiR.sup.169R.sup.170R.sup.171, (OSiR.sup.169R.sup.170).sub.dR.sup.171, or phenyl; R.sup.169, R.sup.170 and R.sup.171 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSi(CH.sub.3).sub.3, or phenyl; and d is an integer from 1 to 10.

6. The compound according to claim 1, wherein ArR.sup.10 and ArR.sup.10 are independently of each other H, F, cyano, C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, ##STR00138## wherein R.sup.3 and R.sup.3 are independently of each other hydrogen, F, C.sub.1-C.sub.25alkyl, or C.sub.1-C.sub.25alkoxy, R.sup.22, R.sup.23, R.sup.25, R.sup.26, R.sup.27, R.sup.28 and R.sup.29 to R.sup.33 represent independently of each other H, F, cyano, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more F, or C.sub.1-C.sub.25alkyl, and R.sup.24 is H, F, cyano, NO.sub.2, NR.sup.112R.sup.113, phenyl, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkylthio, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, or C.sub.1-C.sub.25alkyl; X is O, S, Se, or NR.sup.8, X.sup.5 is O, S, Se, or NR.sup.59, R.sup.58 is H, F, cyano, phenyl, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkylthio, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, or C.sub.1-C.sub.25alkyl; R.sup.8 and R.sup.59 are hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted one to three times by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more F; or C.sub.7-C.sub.25arylalkyl, and R.sup.112 and R.sup.113 are independently of each other hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted one to three times by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more F; or C.sub.7-C.sub.25arylalkyl.

7. The compound according to claim 1, which is a compound of formula ##STR00139## wherein U.sub.1 and U.sup.2 are O, T.sup.1 and T.sup.2 are H, a C.sub.1-C.sub.38alkyl group which can optionally be interrupted by O, S, or NR.sup.1, wherein R.sup.60 is C.sub.1-C.sub.25alkyl, or phenylC.sub.1-C.sub.4alkyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy, T.sup.3 and T.sup.4 are H, a C.sub.1-C.sub.38alkyl group can optionally be interrupted by O, S, or NR.sup.60, wherein R.sup.60 is C.sub.1-C.sub.25alkyl, or phenylC.sub.1-C.sub.4alkyl, which can be substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy, and ArR.sup.10 and ArR.sup.10 are independently of each other H, F, cyano, C.sub.1-C.sub.25alkyl substituted with one or more fluorine atoms, C.sub.1-C.sub.25alkyl, ##STR00140## wherein R.sup.3 and R.sup.3 are independently of each other hydrogen, F, C.sub.1-C.sub.25alkyl, or C.sub.1-C.sub.25alkoxy, R.sup.22, R.sup.23, R.sup.25, R.sup.26, R.sup.27, R.sup.28 and R.sup.29 to R.sup.33 represent independently of each other H, F, cyano, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more F, or C.sub.1-C.sub.25alkyl, and R.sup.24 is H, F, cyano, NO.sub.2, NR.sup.112R.sup.113, CF.sub.3, phenyl, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, or C.sub.1-C.sub.25alkyl; X is O, S, Se, or NR.sup.8, X.sup.5 is O, S, Se, or NR.sup.59, R.sup.58 is H, F, cyano, phenyl, C.sub.1-C.sub.25alkoxy, C.sub.1-C.sub.25alkylthio, C.sub.1-C.sub.25alkyl substituted with one or more halogen atoms, or C.sub.1-C.sub.25alkyl; R.sup.8 and R.sup.59 are hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted one to three times by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more F, or C.sub.7-C.sub.25arylalkyl, and R.sup.112 and R.sup.113 are independently of each other hydrogen, C.sub.6-C.sub.18aryl, C.sub.6-C.sub.18aryl which is substituted one to three times by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms and/or is optionally substituted by one or more F, or C.sub.7-C.sub.25arylalkyl.

8. The compound according to claim 1, which is a compound of formula ##STR00141## ##STR00142## ##STR00143##

9. A polymer comprising a repeating unit of the formula [(Ar)Y(Ar).sub.z.sup.2](V), wherein z.sup.1 and z.sup.2 are independently of each other 0, or 1, Y, Ar and Ar are defined in claim 1.

10. The polymer according to claim 9, comprising a repeating unit of the formula ##STR00144## wherein z.sup.1 and z.sup.2 are independently of each other 0, or 1.

11. The polymer according to claim 9, comprising a repeating unit of the formula ##STR00145##

12. The polymer according to claim 9, wherein U.sup.1 and U.sup.2 are O.

13. The polymer according to claim 9, wherein T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are H, a C.sub.1-C.sub.38alkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, or E.sub.Si, and/or can optionally be interrupted by O, S, wherein E.sub.Si is SiR.sup.161R.sup.162R.sup.163; R.sup.161, R.sup.162 and R.sup.163 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.6cycloalkyl, which might optionally be substituted with C.sub.1-C.sub.4alkyl; C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSiR.sup.164R.sup.165R.sup.166, (OSiR.sup.164R.sup.165).sub.dR.sup.166, or phenyl; R.sup.164, R.sup.165 and R.sup.166 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSiR.sup.169R.sup.170R.sup.171, (OSiR.sup.169R.sup.170).sub.dR.sup.171, or phenyl; R.sup.169, R.sup.170 and R.sup.171 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8haloalkyl, C.sub.2-C.sub.8alkenyl, OSi(CH.sub.3).sub.3, or phenyl; d is an integer from 1 to 10.

14. The polymer according to claim 9, wherein Ar and Ar are independently of each other a single bond, ##STR00146## wherein R.sup.3 and R.sup.3 are independently of each other hydrogen, F, C.sub.1-C.sub.25alkoxy, or C.sub.1-C.sub.25alkyl, R.sup.8 is hydrogen, or C.sub.1-C.sub.25alkyl, and R.sup.104 and R.sup.104 are independently of each other hydrogen, cyano, COOR.sup.103, or a C.sub.1-C.sub.25alkyl group, wherein R.sup.103 is a C.sub.1-C.sub.25alkyl group, which can optionally be interrupted by O, or S.

15. The polymer according to claim 9, comprising a repeating unit of the formula *A* and a repeating unit *COM.sup.1*, wherein A is a repeating unit of formula (V), and COM.sup.1- is a repeating unit, which has the meaning of Ar.sup.2, or a group of formula ##STR00147## wherein s is 1, t is 1, u is 0 or 1, v is 0 or 1, and Ar.sup.4 and Ar.sup.5 are independently of each other a group of formula ##STR00148## wherein Ar.sup.14, Ar.sup.15, Ar.sup.16 and Ar.sup.17 are independently of each other a group of formula ##STR00149## wherein one of X.sup.7 and X.sup.8 is N and the other is CR.sup.14, R.sup.14, R.sup.14, R.sup.17 and R.sup.17 are independently of each other H, F, a C.sub.1-C.sub.52alkyl group, or a C.sub.1-C.sub.25alkoxy group, R.sup.200 and R.sup.200 are independently of each other H, or F, R.sup.201 and R.sup.202 are independently of each other H, a C.sub.1-C.sub.100alkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.2-C.sub.100alkenyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.3-C.sub.100alkinyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.3-C.sub.12cycloalkyl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si; and/or can optionally be interrupted by O, S, NR.sup.60, CONR.sup.60, NR.sup.60CO, COO, CO or OCO, a C.sub.6-C.sub.24aryl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si, a C.sub.2-C.sub.20heteroaryl group which can optionally be substituted one or more times with C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, halogen, C.sub.5-C.sub.12cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20heteroaryl, or E.sub.Si, R.sup.60 is hydrogen, C.sub.1-C.sub.18haloalkyl, C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C.sub.1-C.sub.18alkanoyl, or C.sub.7-C.sub.25arylalkyl, R.sup.206 is hydrogen, or C.sub.1-C.sub.25alkyl, or C.sub.6-C.sub.18aryl; C.sub.6-C.sub.15aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, and R.sup.304 and R.sup.304 are independently of each other hydrogen, cyano, COOR.sup.305, or a C.sub.1-C.sub.25alkyl group, wherein R.sup.305 is a C.sub.1-C.sub.25alkyl group, which can optionally be interrupted by O, or S.

16. The polymer according to claim 9, which is a polymer of the formula ##STR00150## ##STR00151## ##STR00152## ##STR00153##

17. An organic semiconductor material, layer or component, comprising a compound according to claim 1.

18. A semiconductor device, comprising a compound according to claim 1.

19. The semiconductor device according to claim 18, which is an organic photovoltaic device, a photodiode, or an organic field effect transistor.

20. A process for the preparation of an organic semiconductor device, which process comprises applying a solution and/or dispersion of a compound according to claim 1 in an organic solvent to a suitable substrate and removing the solvent.

21. A PV device, photodiode, IR absorber, or organic filed effect transistor, comprising the compound according to claim 1.

22. A compound of formula
X.sup.6ArYArX.sup.6(X), wherein Y, Ar and Ar are defined in claim 1, and X.sup.6 and X.sup.6 are independently of each other halogen, ZnX.sup.12, SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are identical or different and are H or C.sub.1-C.sub.6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X.sup.12 is a halogen atom; or OS(O).sub.2CF.sub.3, OS(O).sub.2-aryl, OS(O).sub.2CH.sub.3, B(OH).sub.2, B(OY.sup.1).sub.2, ##STR00154## BF.sub.4Na, or BF.sub.4K, wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group, Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10 alkylene group, which can optionally be substituted by one, or more C.sub.1-C.sub.8alkyl groups, and Y.sup.13 and Y.sup.14 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl group.

23. The compound according to claim 22, which is a compound of formula ##STR00155## ##STR00156##

24. A process for producing a compound of formula ##STR00157## which process comprises (a) reacting a compound of formula ##STR00158## with a compound of formula T.sub.1COOH (XIIa) and a compound of formula T.sup.2COOH (XIIb), or a compound of formula T.sub.1COOH (XIIa) in a solvent in the presence of an acid and/or an acid anhydride, wherein T.sup.1, T.sup.2, T.sup.3, T.sup.4, U.sup.1, U.sup.2, Ar, Ar, R.sup.10 and R.sup.10 are defined in claim 1 and when compound of formula (XI) is reacted only with a compound of formula (XIIa), T.sup.2 in formula (Ia) has the meaning of T.sup.1.

Description

EXAMPLES

Example 1

Synthesis of dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1a (A-1)) by the Condensation of 2-fromylpyrrole and succinyl chloride

(1) ##STR00088##

(2) Procedure 1.

(3) 2-Formylpyrrole (1.14 g, 12.0 mmol) and 4-dimethylaminopyridine (DMAP, 98 mg, 0.80 mmol) were dissolved in 25 ml of dry dichloromethane. The mixture was stirred under an argon atmosphere and triethylamine (2.2 ml, 15.8 mmol) was added. Then succinyl chloride (0.44 ml, 4.0 mmol) was added dropwise. The stirring was continued for 2 h at room temperature. Reaction mixture contained a large amount of a black tar, which was removed by filtration through Celite. Celite was then washed with dichloromethane. To the combined filtrates water was added and the layers were separated. Aqueous layer was extracted three times with dichloromethane. Combined organic layers were washed twice with water and dried over Na.sub.2SO.sub.4. The drying agent was filtered off and the solvents were evaporated. The product was purified by column chromatography (silica, dichloromethane:acetone 19:1) and recrystallized by slow addition of pentane to the solution of product in small amount of hot chloroform. Compound 1a (32 mg, 3.4% yield) was obtained as brown powder. Mp. >280 C. (decomposition). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.97 (s, 1H, CH (6-membered ring)), 7.81 (dd, J=3.1, 0.7 Hz, 1H, pyrrole: 5-H), 6.80 (dd, J=3.6, 1.2 Hz, 1H, pyrrole: 3-H), 6.54 (t, J=3.4 Hz, 1H, pyrrole: 4-H). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.4, 131.7, 125.2, 123.6, 120.3, 118.4, 116.2. HRMS (EI) calcd for C.sub.14H.sub.8N.sub.2O.sub.2(M.sup.+): 236.0586; found: 236.0580. Elemental analysis calcd (%) for C.sub.14H.sub.8N.sub.2O.sub.2: C, 71.18, H, 3.41, N, 11.86; found: C, 71.19, H, 3.60, N, 11.65.

(4) In addition to the dye 1a, unreacted 2-formylpyrrole (0.74 g, 65% of the initial amount) was also separated from the reaction mixture.

(5) Procedure 2.

(6) A mixture consisting of 2-formylpyrrole (238 mg, 2.5 mmol), powdered potassium carbonate (1.38 g, 10.0 mmol) and 10 ml of dry DMF was stirred under an argon atmosphere at 0 C. The solution of succinyl chloride (110 l, 1.0 mmol) in 1.0 ml of dry dichloromethane was added dropwise. The stirring was continued for 2 h at 0 C. The reaction mixture was then diluted with water and passed through Celite, which was washed twice with water. Then two portions of ethanol and three portions of chloroform were passed through Celite in order to recover the product. These filtrates were combined and washed twice with water and dried over Na.sub.2SO.sub.4. The drying agent was filtered off and the solvents were evaporated. The product was recrystallized by slow addition of pentane to its solution in small amount of hot chloroform. Compound 1a (15 mg, 6.4% yield) was obtained as a brown powder. The product was identified by the comparison with previously synthesized sample.

Example 2

Synthesis of dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1a (A-1)) by the Vilsmeier-Haack Formylation of 1,4-di(pyrrol-1-yl)butane-1,4-dione (3)

(7) ##STR00089##

(8) A mixture of succinamide (1.16 g, 10 mmol), 2,5-dimethoxytetrahydrofuran (3.9 ml, 30 mmol), para-toluenesulfonic acid monohydrate (190 mg, 1.0 mmol) and 25 ml of toluene was refluxed for 2 h under the Dean-Stark apparatus. The reaction mixture was cooled and the black precipitate, which was formed in the reaction, was filtered off and washed with chloroform. The filtrates were washed with water three times and dried over Na.sub.2SO.sub.4. Solvents were evaporated and the product was purified by the column chromatography (silica, hexanes:dichloromethane 1:2). The product was recrystallized from ethanol. Compound 3 (632 mg, 29% yield) was obtained as a white powder. Mp. 162-164 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.36 (br s, 4H, pyrrole: 2-H and 5-H), 6.36-6.27 (m, 4H, pyrrole: 3-H and 4-H), 3.34 (s, 4H, CH.sub.2CH.sub.2). .sup.13C NMR (126 MHz, CDCl.sub.3) 168.2, 119.0, 113.5, 28.9. HRMS (EI) calcd for C.sub.12H.sub.12N.sub.2O.sub.2 (M.sup.+): 216.0899; found: 216.0910. Elemental analysis calcd (%) for C.sub.12H.sub.12N.sub.2O.sub.2: C, 66.65, H, 5.59, N, 12.96; found: C, 66.86, H, 5.73, N, 12.92.

(9) ##STR00090##

(10) Under an argon atmosphere, to the solution of compound 3 (432 mg, 2.0 mmol) in 10 ml of dry 1,2-dichloroethane was added DMF (390 l, 5.0 mmol). Then phosphorus(V) oxychloride (480 l, 5.2 mmol) was added dropwise and the mixture was refluxed for 2 h. The reaction was quenched by the addition of saturated aqueous solution of sodium bicarbonate (10 ml). The resulting mixture was stirred for 5 min and diluted with dichloromethane and water. Layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were washed with water and dried over Na.sub.2SO.sub.4. The products were separated by column chromatography (silica, dichloromethane:acetone 19:1). Dye 1a was recrystallized by slow addition of pentane to its solution in small amount of hot chloroform. The product was obtained as a brown powder (39 mg, 8.3% yield) and identified by the comparison with previously synthesized sample. In addition to compound 1a, 2-formylpyrrole (127 mg, 33% yield) was also obtained.

Example 3

Acylation of Compound 3 (A-2) with Acetic Acid

(11) ##STR00091##

(12) Compound 3 (216 mg, 1.0 mmol) was dissolved in 4.5 ml of dry dichloromethane under an argon atmosphere, and the solution was cooled to 0 C. Trifluoroacetic anhydride (3.0 ml, 22 mmol) and acetic acid (460 l, 8.0 mmol) were added and the resulting mixture was stirred at 0 C. for 10 min and then at room temperature for 4 h. The reaction mixture was then poured into a beaker containing 20 ml of saturated aqueous NaHCO.sub.3 and mixed (CO.sub.2 gas evolved). When the evolution of carbon dioxide was no longer observed, layers were separated. Aqueous layer was extracted three times with chloroform, and the combined organic layers were washed with water and dried over Na.sub.2SO.sub.4. Obtained mixture was separated using column chromatography (silica, hexanes:dichloromethane 1:2.fwdarw.pure dichloromethane) to give two crude products, compounds 4 and 1b, which were recrystallized by slow addition of methanol to a hot solution of the dye in small amount of chloroform.

6,12-Dimethyl-3-trifluoroacetyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (4)

(13) Compound 4 (34 mg, 9.4% yield) was obtained as a dark brown powder. Mp. >180 C. (decomposition). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.84 (d, J=1.9 Hz, 1H, DPND: 9-H), 7.19 (d, J=3.9 Hz, 1H, DPND: 1-H), 6.97 (d, J=3.1 Hz, 1H, DPND: 7-H), 6.89 (d, J=4.0 Hz, 1H, DPND: 2-H), 6.56 (t, J=3.4 Hz, 1H, DPND: 8-H), 2.86 (s, 3H, CH.sub.3), 2.81 (s, 3H, CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 174.1-173.5 (m), 158.4, 143.3, 139.4, 137.8, 133.4, 128.4, 124.3, 124.3, 123.9, 119.1, 118.9, 116.0, 116.1 (q, J=290 Hz), 114.80, 114.54, 18.27, 17.81. HRMS (ESI) calcd for C.sub.18H.sub.11F.sub.3N.sub.2O.sub.3Na (M+Na.sup.+): 383.0619; found: 383.0606. Elemental analysis calcd (%) for C.sub.18H.sub.11F.sub.3N.sub.2O.sub.3: C, 60.01, H, 3.08, N, 7.78; found: C, 59.92, H, 3.02, N, 7.68.

6,12-Dimethyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1b)

(14) Compound 1b (33 mg, 12% yield) was obtained as a dark brown powder. Mp. >280 C. (decomposition). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.84 (d, J=1.7 Hz, 2H, pyrrole: 5-H), 6.95-6.85 (m, 2H, pyrrole: 3-H), 6.54 (t, J=3.3 Hz, 2H, pyrrole: 4-H), 2.85 (s, 6H, CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 159.1, 140.5, 133.7, 122.7, 117.1, 115.6, 115.0, 18.3. HRMS (ESI) calcd for C.sub.16H.sub.12N.sub.2O.sub.2Na (M+Na.sup.+): 287.0796; found: 287.0786. Elemental analysis calcd (%) for C.sub.16H.sub.12N.sub.2O.sub.2: C, 72.72, H, 4.58, N, 10.60; found: C, 72.79, H, 4.50, N, 10.62.

Example 4

General Procedure for the Preparation of 6,12-Disubstituted DPND Derivatives (1b-1e)

(15) Compound 3 (108 mg, 0.50 mmol) was dissolved in 3.0 ml of dry dichloromethane under an argon atmosphere, and the solution was cooled to 0 C. Subsequently, to the reaction flask were slowly added: carboxylic acid (3.0 mmol), trifluoroacetic anhydride (830 l, 6.0 mmol) and trifluoroacetic acid (230 l, 3.0 mmol). The resulting mixture was stirred at room temperature for given time. The reaction mixture was then slowly poured into a beaker containing 20 ml of vigorously stirred saturated aqueous NaHCO.sub.3 (CO.sub.2 evolved). When the evolution of carbon dioxide was no longer observed, the mixture was diluted with chloroform and layers were separated. Aqueous layer was extracted four times with chloroform, and the combined organic layers were washed with water and dried over Na.sub.2SO.sub.4. The product was purified by column chromatography and recrystallized (see below for details).

(16) ##STR00092##

6,12-Dimethyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1b (A-2))

(17) Carboxylic acid used: acetic acid (172 l, 3.0 mmol). Reaction time: 5 h. Product was purified using column chromatography (silica, dichloromethane) and recrystallized by slow addition of methanol to a hot solution of the dye in small amount of chloroform. Compound 1b (23 mg, 17% yield) was obtained as a dark brown powder and identified by the comparison with previously synthesized sample.

(18) ##STR00093##

6,12-Diheptyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1c (A-3))

(19) Carboxylic acid used: caprylic acid (475 l, 3.0 mmol). Reaction time: 3 h. Product was purified using column chromatography (silica, hexanes:dichloromethane 2:1.fwdarw.1:1) and recrystallized by slow addition of methanol to a solution of the dye in small amount of dichloromethane. Compound 1c (63 mg, 29% yield) was obtained as a red solid. Mp. 107-109 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.84 (dd, J=3.0, 1.3 Hz, 2H, pyrrole: 5-H), 6.87 (dd, J=3.7, 1.3 Hz, 2H, pyrrole: 3-H), 6.54 (t, J=3.4 Hz, 2H, pyrrole: 4-H), 3.35-3.22 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.76-1.62 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.58-1.47 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.44-1.35 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.35-1.23 (m, 8H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.89 (t, J=6.9 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.6, 145.6, 133.4, 122.6, 116.7, 115.6, 114.6, 32.1, 31.2, 30.6, 30.5, 29.4, 22.8, 14.3. HRMS (ESI) calcd for C.sub.28H.sub.37N.sub.2O.sub.2 (M+H.sup.+): 433.2855; found: 433.2848. Elemental analysis calcd (%) for C.sub.28H.sub.36N.sub.2O.sub.2: C, 77.74, H, 8.39, N, 6.48; found: C, 77.48, H, 8.48, N, 6.33.

(20) The synthesis of compound 1c was repeated in 10-times larger scale, using the same procedure and following amounts of reagents: compound 3 (1.08 g, 5.00 mmol), caprylic acid (4.75 ml, 30 mmol), trifluoroacetic anhydride (8.3 ml, 60 mmol), trifluoroacetic acid (2.30 ml, 30 mmol) and dichloromethane (30 ml) as a solvent. After 3.5 h of the reaction at room temperature 525 mg of product 1c was obtained (23% yield).

(21) ##STR00094##

6,12-Di-sec-butyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1d (A-4))

(22) Carboxylic acid used: 2-methylbutyric acid (330 l, 3.0 mmol). Reaction time: 6 h. Product was purified using column chromatography (silica, hexanes:dichloromethane 1:1) and recrystallized by slow addition of methanol to a solution of the dye in small amount of dichloromethane. Compound 1d (36 mg, 21% yield) was obtained as red crystals. Mp. 176-178 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.79 (dd, J=2.9, 1.0 Hz, 2H, pyrrole: 5-H), 7.01 (d, J=3.0 Hz, 2H, pyrrole: 3-H), 6.50 (t, J=3.4 Hz, 2H, pyrrole: 4-H), 4.74 (br s, 2H, C(CH.sub.3)CH.sub.2CH.sub.3), 2.00-1.90 (m, 2H, CH(CH.sub.3)CH.sub.2CH.sub.3), 1.90-1.79 (m, 2H, CH(CH.sub.3)CH.sub.2CH.sub.3), 1.46 (dd, J=7.1, 1.7 Hz, 6H, CH(CH.sub.3)CH.sub.2CH.sub.3), 0.96 (t, J=7.4 Hz, 6H, CH(CH.sub.3)CH.sub.2CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 159.7, 150.7, 130.3, 121.6, 118.7, 116.8, 115.2, 35.9, 30.6, 20.5, 13.1. HRMS (ESI) calcd for C.sub.22H.sub.24N.sub.2O.sub.2Na (M+Na.sup.+): 371.1735; found: 371.1724. Elemental analysis calcd (%) for C.sub.22H.sub.24N.sub.2O.sub.2: C, 75.83, H, 6.94, N, 8.04; found: C, 75.63, H, 6.89, N, 7.94.

(23) ##STR00095##

6,12-Bis(4-methoxybenzyl)dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1e (A-5))

(24) Carboxylic acid used: 4-methoxyphenylacetic acid (499 mg, 3.0 mmol). Reaction time: 6 h. Product was purified using column chromatography (silica, dichloromethane.fwdarw.dichloromethane:ethyl acetate 19:1) and recrystallized by slow addition of methanol to a solution of the dye in small amount of chloroform. Compound 1e (25 mg, 10.5% yield) was obtained as red crystals. Mp. >270 C. (decomposition). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.82 (dd, J=3.0, 1.2 Hz, 2H, pyrrole: 5-H), 7.24-7.18 (AABB, 4H, benzene: 2-H and 6-H), 6.91 (dd, J=3.7, 1.2 Hz, 2H, pyrrole: 3-H), 6.83-6.78 (AABB, 4H, benzene: 3-H and 5-H), 6.52 (t, J=3.4 Hz, 2H, pyrrole: 4-H), 4.69 (s, 4H, CH.sub.2Ar), 3.75 (s, 6H, OCH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.2, 158.0, 142.4, 133.6, 130.8, 129.3, 123.1, 118.2, 115.8, 115.3, 113.9, 55.2, 34.7. HRMS (ESI) calcd for C.sub.30H.sub.24N.sub.2O.sub.4Na (M+Na.sup.+): 499.1634; found: 499.1624. Elemental analysis calcd (%) for C.sub.30H.sub.24N.sub.2O.sub.4: C, 75.62, H, 5.08, N, 5.88 found: C, 75.65, H, 5.10, N, 5.92.

(25) ##STR00096##

6,12-Diethyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1f (A-6))

(26) Compound 3 (216 mg, 1.0 mmol) was dissolved in 6.0 ml of dry dichloromethane under an argon atmosphere, and the solution was cooled to 0 C. Subsequently, to the reaction flask were slowly added: propionic anhydride (380 l, 3.0 mmol), trifluoroacetic anhydride (1.10 ml, 7.9 mmol) and trifluoroacetic acid (920 l, 12.0 mmol). The resulting mixture was stirred at room temperature for 2 h. The reaction mixture was then slowly poured into a beaker containing 20 ml of vigorously stirred saturated aqueous NaHCO.sub.3 (CO.sub.2 evolved). When the evolution of carbon dioxide was no longer observed, the mixture was diluted with chloroform and layers were separated. Aqueous layer was extracted four times with chloroform, and the combined organic layers were washed with water and dried over Na.sub.2SO.sub.4. The product was purified by column chromatography (silica, toluene) and recrystallized by slow addition of methanol to the solution of product in small amount of dichloromethane. Compound 1f (67 mg, 23%) was obtained as dark red crystals. Mp. 226-229 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.84 (dd, J=3.0, 1.3 Hz, 2H, pyrrole: 5-H), 6.89 (dd, J=3.6, 1.3 Hz, 2H, pyrrole: 3-H), 6.55 (t, J=3.4 Hz, 2H, pyrrole: 4-H), 3.33 (q, J=7.4 Hz, 4H, CH.sub.2CH.sub.3), 1.35 (t, J=7.4 Hz, 6H, CH.sub.2OCH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.5, 146.8, 133.0, 122.7, 116.7, 115.7, 114.5, 24.4, 14.5. HRMS (ESI) calcd for C.sub.18H.sub.16N.sub.2O.sub.4Na (M+Na.sup.+): 315.1109; found: 315.1097.

Synthesis of Various 6,12-Disubstituted DPND Derivatives.[a]

(27) ##STR00097##

(28) TABLE-US-00003 Carboxylic acid Reaction time Product T.sup.1 Yield CH.sub.3CO.sub.2H 5 h 1b (A-2) CH.sub.3 17% C.sub.7H.sub.15CO.sub.2H 3 h.sup.[c] 1c (A-3) C.sub.7H.sub.15 29%.sup.[c] 3.5 h.sup.[d] 23%.sup.[d] 6 h Id (A-4) sec-butyl 21% 6 h le (A-5) 4-methoxybenzyl 10.5% (C.sub.2H.sub.5CO).sub.2O .sup.[b] 2 h 1f (A-6) C.sub.2H.sub.5 23% [a] Reagents proportions: 3 (0.5 mmol), carboxylic acid (3 mmol), TFAA (6 mmol), TFA (3 mmol). .sup.[b] Propionic anhydride used instead of carboxylic acid. .sup.[c]0.5 mmol scale. .sup.[d]5.0 mmol scale.

Example 4

3,9-Dibromo-6,12-diheptyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (5 (C-1))

(29) ##STR00100##

(30) A solution of compound 1c (108 mg, 0.25 mmol) in 5 ml of chloroform was stirred at 0 C. (water-ice bath). Freshly recrystallized N-bromosuccinimide (93 mg, 0.52 mmol) was added and the obtained mixture was stirred in the darkness (protection with aluminium foil) for 16 h. During this time ice in the ice bath melted and the reaction mixture warmed to the room temperature. The reaction mixture was diluted with chloroform, washed with water three times, and dried over Na.sub.2SO.sub.4. The product was purified using column chromatography (silica, hexanes:dichloromethane 3:1.fwdarw.2:1) and recrystallized by slow addition of methanol to a solution of the dye in small amount of dichloromethane. Compound 5 (107 mg, 72% yield) was obtained as a red solid. Mp. 133-135 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 6.81 (d, J=4.0 Hz, 2H, pyrrole: 3-H), 6.59 (d, J=4.0 Hz, 2H, pyrrole: 4-H), 3.24-3.05 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.71-1.59 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.55-1.46 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.41-1.23 (m, 12H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.89 (t, J=6.8 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.9, 143.3, 135.0, 120.5, 115.8, 115.4, 106.6, 31.9, 30.3, 30.2 (2 signals), 29.2, 22.7, 14.1. HRMS (ESI) calcd for C.sub.28H.sub.34Br.sub.2N.sub.2O.sub.2 (M.sup.+): 588.0987; found: 588.0985. Elemental analysis calcd (%) for C.sub.28H.sub.34Br.sub.2N.sub.2O.sub.2: C, 56.96, H, 5.80, N, 4.74; found: C, 56.98, H, 5.77, N, 4.76.

(31) The synthesis of compound 5 was repeated in 4-times larger scale, using the same procedure and following amounts of reagents: compound 1c (433 mg, 1.00 mmol), N-bromosuccinimide (374 mg, 2.10 mmol) and chloroform (15 ml) as a solvent. 379 mg of the product 5 was obtained (64% yield).

Example 5

3,9-Dicyano-6,12-diheptyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (6 (A-7))

(32) ##STR00101##

(33) A mixture of compound 5 (59 mg, 0.10 mmol), copper(I) cyanide (20 mg, 0.22 mmol) and 2 ml of dry NMP was stirred under argon at 140 C. for 16 h and at 160 C. for 5 h. The mixture was diluted with water and passed through Celite, which was washed with water. Then the product was extracted from Celite with one portion of ethanol and three portions of chloroform. The organic filtrates were combined, washed with water twice and dried over Na.sub.2SO.sub.4. Product was purified by column chromatography (silica, hexanes:dichloromethane 2:3). After evaporation of eluent 16 mg of product was obtained (33% yield), which was recrystallized by slow addition of methanol to warm solution of the dye in small amount of chloroform. Compound 6 (11 mg, 23% yield) was obtained as red crystals. Mp. 222-225 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.19 (d, J=4.0 Hz, 2H, pyrrole: 3-H), 6.92 (d, J=4.0 Hz, 2H, pyrrole: 4-H), 3.43-3.15 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.76-1.62 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.59-1.47 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.42-1.25 (m, 12H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.90 (t, J=6.8 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 156.8, 146.6, 136.2, 127.0, 116.9, 116.0, 112.5, 106.4, 31.8, 31.1, 30.2, 30.1, 29.1, 22.7, 14.1. HRMS (ESI) calcd for C.sub.30H.sub.34N.sub.4O.sub.2Na (M+Na.sup.+): 505.2579; found: 505.2574.

Example 6

General Procedure for the Sonogashira Coupling of Compound 5 (C-1) with Para-Substituted PhenylacetylenesSynthesis of Compounds 7a-d

(34) ##STR00102##

(35) In a Schlenck flask containing a magnetic stirring bar were placed: bromoderivative 5 (0.10 mmol, 59 mg), copper(I) iodide (1.9 mg, 0.010 mmol), tetrakis(triphenylphosphine)palladium(0) (5.8 mg, 0.005 mmol), and para-substituted phenylacetylene (0.30 mmol). The vessel was evacuated and backfilled with argon (3 times) and anhydrous, degassed THF was added (3 ml) followed by dry triethylamine (56 l, 0.40 mmol). The vessel was tightly closed and again carefully evacuated (until the mixture start to boil) and backfilled with argon (3 times). The content of the flask was stirred for 20 h at 70 C. (above the boiling point). Solvents were evaporated and the product was purified as described below.

6,12-Diheptyl-3,9-bis((4-nitrophenyl)ethynyl)dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (7a (A-8))

(36) Prepared from 4-nitrophenylacetylene (44 mg, 0.30 mmol). Product was purified using column chromatography (silica, hexanes:dichloromethane 1:1.fwdarw.1:2) and recrystallized from toluene. Compound 7a (56 mg, 78% yield) was obtained as a dark violet powder. Mp. >400 C. .sup.1H NMR (500 MHz, CDCl.sub.3, 50 C.) 8.26-8.18 (AABB, 4H, benzene: 3-H and 5-H), 7.77-7.67 (AABB, 4H, benzene: 2-H and 6-H), 6.89 (s, 4H, pyrrole: 3-H and 4-H), 3.34-3.27 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.80-1.69 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.61-1.54 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.44-1.23 (m, 12H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.90 (t, J=6.9 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3, 50 C.) 158.4, 147.5, 144.3, 135.5, 132.2, 130.3, 123.8, 118.6, 116.9, 116.3, 96.2, 88.1, 32.1, 31.0, 30.5 (2 signals), 29.2, 22.8, 14.2. Elemental analysis calcd (%) for C.sub.44H.sub.42N.sub.4O.sub.6: C, 73.11, H, 5.86, N, 7.75; found: C, 73.20, H, 5.93, N, 7.71.

6,12-Diheptyl-3,9-bis((4-(trifluoromethyl)phenyl)ethynyl)dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (7b (A-9))

(37) Prepared from 4-(trifluoromethyl)phenylacetylene (51 mg, 0.30 mmol). Product was purified using column chromatography (silica, hexanes:dichloromethane 4:1.fwdarw.3:7) and recrystallized by slow addition of methanol to hot solution of the dye in small amount of chloroform. Compound 7b (44 mg, 57% yield) was obtained as a dark green powder. Mp. 200-203 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.76-7.67 (AABB, 4H, benzene: 3-H and 5-H), 7.67-7.58 (AABB, 4H, benzene: 2-H and 6-H), 6.89 (d, J=4.0 Hz, 2H, pyrrole: 3-H), 6.87 (d, J=4.0 Hz, 2H, pyrrole: 4-H), 3.34-3.23 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.77-1.68 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.59-1.52 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.48-1.40 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.38-1.29 (m, 8H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.89 (t, J=7.0 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.5, 144.0, 135.1, 131.8, 125.5, 125.4, 123.4, 118.8, 116.6, 116.1, 96.5, 85.2, 32.1, 30.9, 30.5, 29.9, 29.2, 22.8, 14.3 (signals of CF.sub.3 group and adjacent carbon atom were not identified due to low intensities caused by .sup.13C-.sup.19F coupling). HRMS (ESI) calcd for C.sub.46H.sub.42F.sub.6N.sub.2O.sub.2(M.sup.+): 768.3150; found: 768.3153.

6,12-Diheptyl-3,9-bis((4-methoxyphenyl)ethynyl)dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (7c (A-10))

(38) Prepared from 4-methoxyphenylacetylene (40 mg, 0.30 mmol). Product was purified using column chromatography (silica, hexanes:dichloromethane 3:2.fwdarw.5:4) and recrystallized by slow addition of methanol to solution of the dye in small amount of dichloromethane. Compound 7c (33 mg, 48% yield) was obtained as a dark violet powder. Mp. 185-187 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.64-7.48 (AABB, 4H, benzene: 2-H and 6-H), 6.95-6.87 (AABB, 4H, benzene: 3-H and 5-H), 6.84 (d, J=4.0 Hz, 2H, pyrrole: 3-H), 6.77 (d, J=3.9 Hz, 2H, pyrrole: 4-H), 3.85 (s, 6H, OCH.sub.3), 3.34-3.21 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.78-1.66 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.60-1.51 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.48-1.39 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.39-1.27 (m, 8H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.90 (t, J=6.5 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH.sub.3). .sup.13C NMR (126 MHz, CDCl.sub.3) 160.0, 158.6, 143.3, 134.3, 133.2, 122.1, 119.7, 116.0, 115.8, 115.5, 114.1, 98.3, 81.9, 55.3, 32.0, 30.7, 30.3, 29.0, 22.7, 14.2. HRMS (ESI) calcd for C.sub.46H.sub.48N.sub.2O.sub.4Na (M+Na.sup.+): 715.3512; found: 715.3506.

3,9-Bis((4-(dimethylamino)phenyl)ethynyl)-6,12-diheptyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (7d (A-11))

(39) Prepared from 4-(dimethylamino)phenylacetylene (44 mg, 0.30 mmol). Product was purified using column chromatography (silica, hexanes:dichloromethane 1:1.fwdarw.1:3) and recrystallized by slow addition of methanol to solution of the dye in small amount of dichloromethane. Compound 7d (40 mg, 56% yield) was obtained as a black powder. Mp. 235-239 C. .sup.1H NMR (500 MHz, CDCl.sub.3) 7.57-7.46 (AABB, 4H, benzene: 2-H and 6-H), 6.83 (d, J=4.0 Hz, 2H, pyrrole: 3-H), 6.74 (d, J=4.0 Hz, 2H, pyrrole: 4-H), 6.73-6.59 (m, 4H, benzene: 3-H and 5-H), 3.32-3.23 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 3.02 (s, 12H, NCH.sub.3), 1.77-1.68 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.59-1.52 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.47-1.40 (m, 4H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 1.37-1.30 (m, 8H, CH.sub.2(CH.sub.2).sub.5CH.sub.3), 0.90 (t, J=6.8 Hz, 6H, CH.sub.2(CH.sub.2).sub.5CH). .sup.13C NMR (126 MHz, CDCl.sub.3) 158.7, 150.2, 142.8, 134.0, 132.9, 121.5, 120.2, 115.8, 111.9, 99.9, 81.8, 40.3, 32.1, 30.7, 30.4, 29.1, 22.7, 14.2. HRMS (ESI) calcd for C.sub.48H.sub.55N.sub.4O.sub.2 (M+H.sup.+): 719.4325; found: 719.4325. Elemental analysis calcd (%) for C.sub.48H.sub.54N.sub.4O.sub.2: C, 80.19, H, 7.57, N, 7.79; found: C, 80.08, H, 7.50, N, 7.72.

Example 7

Synthesis of 1,4-di(pyrrol-1-yl)butane-1,4-dione (3), Modified Procedure

(40) ##STR00103##

(41) To a solution of pyrrole (0.54 mL, 7.74 mmol) in THF (20 mL) was added n-butyllithium (2.94 mL, 2.7 M in hexane, 7.94 mmol) at 40 C. After stirring for 15 min at 0 C. the solution was again cooled to 40 C. and succinylchloride (0.43 mL, 3.91 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 3 h, quenched with water (10 mL) and then poured onto water (150 mL). The product precipitated as a beige powder and was used in the next step without further purification.

Synthesis of 6,12-Dinonyldipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (1g (A-16))

(42) ##STR00104##

(43) Compound 1g was made according to the general procedure given for compounds 1a-1e: compound 3 (3.00 g, 14 mmol), decanoic acid (14.34 g, 83.0 mmol), trifluoroacetic anhydride (34.97 g, 166 mmol), trifluoroacetic acid (9.49 g, 83 mmol), methylenechloride 90 ml. Reaction time: 15 h. Product was purified using column chromatography over silica gel. Compound 1g was obtained as a red solid. .sup.1H NMR (300 MHz, CDCl.sub.3) 7.84 (dd, 2H), 6.88 (dd, 2H), 6.54 (t, 2H), 3.35-3.25 (m, 4H), 1.71-1.61 (m, 4H), 1.58-1.45 (m, 4H), 1.42-1.12 (m, 20H), 0.93-0.80 (t, 6H).

Example 8

Synthesis of Compound (1h (A-17))

(44) ##STR00105##

(45) Compound 1h was made according to the general procedure given for compounds 1a-1e from compound 3, 4-octyl-tetradecanoic acid [1448593-51-8], trifluoroacetic anhydride, trifluoroacetic acid. Reaction time: 15 h. Product was purified using column chromatography over silica gel.

Example 9

Synthesis of Compound (1i (A-18))

(46) ##STR00106##

(47) Compound 1i was made according to the general procedure given for compounds 1a-1e from compound 3, dodecanoic acid, trifluoroacetic anhydride, trifluoroacetic acid. Reaction time: 15 h. Product was purified using column chromatography over silica gel.

Example 10

Synthesis of Compound (5a (C-6))

(48) ##STR00107##

(49) Compound 5a was made according to the general procedure given for compounds 5 from compound 1i, and NBS. Product was purified using column chromatography over silica gel.

Example 11

General Procedure for the Synthesis of Compounds 8a and 8b

(50) In a Schlenck flask containing a magnetic stirring bar were placed: compound 5a (C-6) (0.1 mmol, 72.6 mg, 1.0 eq), palladium(II) acetate (2.2 mg, 0.01 mmol, 10 mol %), tri(o-tolyl)phosphine (6.1 mg, 0.02 mmol, 20 mol %). The vessel was evacuated and backfilled with argon (3 times) and anhydrous, degassed DMF was added (6 ml) followed by argonated (i-Pr).sub.2NEt (Hnig's base) (0.1 mL) and styrene (0.4 mmol, 4.0 eq). The vessel was tightly closed and again carefully evacuated and backfilled with argon (3 times). The content of the flask was stirred at 90 C. for 24 h. All volatiles were evaporated and the product was purified as described below.

(51) ##STR00108##

3,9-Bis((E)-4-cyanostyryl)-6,12-diundecyl-5H,11H-dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (8a (A-19))

(52) Prepared from 4-cynanostyrene (51.7 mg, 0.4 mmol). Product was purified using column chromatography (SiO.sub.2, cyclohexane:dichloromethane 1:1 then 1:2) and recrystallized by slow addition of methanol to hot solution of the dye in small amount of chloroform. Compound 8a (44.7 mg, 56% yield) was obtained as a dark brown crystals. .sup.1H NMR (500 MHz, CDCl.sub.3) 8.50 (d, 2H, J=13.2 Hz), 7.63 (m, 8H), 7.06 (d, 2H, J=16.4 Hz), 6.95 (d, 2H, J=4.0 Hz), 6.91 (d, 2H, J=4.1 Hz), 3.25 (t, 4H, J=7.7 Hz), 1.69 (m, 4H), 1.56 (m, 4H+H.sub.2O in CDCl.sub.3), 1.41 (m, 4H,) 1.30 (m, 24H+solvents residues), 0.88 (t, 6H, J=6.5 Hz). .sup.13C NMR (125 MHz, CDCl.sub.3) 160.7, 143.3, 141.7, 138.9, 135.5, 132.5, 128.9, 127.1, 123.4, 119.0, 116.7, 115.8, 114.9, 110.7, 31.9, 30.7, 30.5, 30.3, 29.7, 29.7, 29.5, 29.4, 22.7, 14.1. HRMS (EI) calcd for C.sub.54H.sub.62N.sub.4O.sub.2 798.4873 [M.sup.+], found 798.4851.

(53) ##STR00109##

3,9-Bis((E)-3-methoxystyryl)-6,12-diundecyl-5H,11H-dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (8b (A-20))

(54) Prepared from 3-methoxystyrene (53.7 mg, 0.4 mmol, 55.5 L). Product was purified using column chromatography (SiO.sub.2, cyclohexane:dichloromethane 3:2). The obtained fraction was washed with methanol until the washings were colorless to give sufficiently pure compound. Compound 8b (41.3 mg, 51% yield) was obtained as a dark brown crystals.

(55) .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2) 8.35 (d, 2H, J=13.2 Hz), 7.30 (t, 2H, J=6.0 Hz), 7.17 (d, 2H, J=6.0 Hz), 7.08 (t, 4H, J=8.7 Hz), 6.92 (m, 4H), 7.08 (d, 2H, J=6.4 Hz), 3.80 (s, 6H), 3.26 (t, 4H, J=6.0 Hz), 1.70 (m, 4H), 1.55 (m, 4H), 1.40 (m, 4H,) 1.28 (m, 24H+solvents residues), 0.88 (t, 6H, J=5.6 Hz). .sup.13C NMR (125 MHz, CD.sub.2Cl.sub.2) 171.9, 161.3, 160.5, 143.1, 140.0, 139.2, 135.4, 131.2, 130.0, 120.8, 119.7, 116.8, 115.9, 114.3, 113.9, 112.5, 55.6, 32.3, 31.0, 30.9, 30.7, 30.1, 30.1, 29.9, 29.8, 23.1, 14.3. HRMS (EI) calcd for C.sub.54H.sub.68N.sub.2O.sub.4 808.5179 [M.sup.+], found 808.5165.

Example 12

General Procedure for the Direct Coupling of DPND and Bromoarenes

(56) ##STR00110##

(57) In a Schlenk flask containing a magnetic stirring bar were placed: compound 1c (A-3) (0.1 mmol, 43.3 mg, 1.0 eq), palladium(II) acetate (1.1 mg, 0.005 mmol, 5 mol %), PCy.sub.3.HBF.sub.4 (3.7 mg, 0.01 mmol, 10 mol %), pivalic acid (3.1 mg, 0.03 mmol, 30% mol), K.sub.2CO.sub.3 (55.2 mg, 0.4 mmol, 4.0 eq) and, if a solid, the bromoarene (0.25 mmol, 2.5 eq). The vessel was evacuated and backfilled with argon (3 times). If the bromoarene (0.25 mmol, 2.5 eq) was a liquid, it was added next using a syringe followed by anhydrous, degassed toluene (3 mL). The vessel was tightly closed and again carefully evacuated and backfilled with argon (3 times). The content of the flask was stirred at 120 C. for typically 24-72 h. After indicated time the flask was cooled down to room temperature and extracted three times with dichloromethane (325 mL), then dried over magnesium sulphate. All solvents were evaporated off and the residue was purified by column chromatography.

(58) ##STR00111##

4,4-(6,12-diheptyl-5,11-dioxo-5H,11H-dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-3,9-diyl)dibenzonitrile (9a (A-21))

(59) Prepared using 4-bromocyanobenzene (45.5 mg, 0.25 mmol). Product was purified using column chromatography (SiO.sub.2, n-hexane:dichloromethane 1:3) and recrystallized by slow addition of methanol to hot solution of the dye in small amount of chloroform. Compound (47.8 mg, 64% yield) was obtained as a dark brown crystals. R.sub.f=0.42 (SiO.sub.2, n-hexane/DCM, 1:3). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.68 (d, 4H, J=8.5 Hz), 7.56 (d, 4H, J=8.5 Hz), 6.92 (d, 2H, J=3.5 Hz), 6.59 (d, 2H, J=4.0 Hz), 3.20-3.17 (m, 4H), 1.71-1.67 (m, 4H), 1.50-1.44 (m, 4H,) 1.37-1.29 (m, 12H), 0.88 (t, 6H, J=6.5 Hz). .sup.13C NMR (125 MHz, CDCl.sub.3) 159.4, 144.2, 137.9, 137.3, 136.0, 131.4, 129.2, 119.5, 118.9, 116.0, 115.9, 111.2, 31.8, 30.5, 30.4, 30.1, 29.1, 22.7, 14.1. HRMS (ESI) calcd for C.sub.42H.sub.43N.sub.4O.sub.2 635.3386 [M+H.sup.+], found 635.3383.

(60) ##STR00112##

6,12-diheptyl-3,9-bis(4-nitrophenyl)-5H,11H-dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (9b (A-22))

(61) Prepared using 4-bromonitrobenzene (43.3 mg, 0.25 mmol). Product was purified using column chromatography (SiO.sub.2, cyclohexane:dichloromethane 1:1) and recrystallized from toluene. Compound (42.2 mg, 62% yield) was obtained as a dark brown crystals. R.sub.f=0.30 (SiO.sub.2, cyclohexane/DCM, 1:1). .sup.1H NMR (500 MHz, CDCl.sub.3) 8.26 (d, 4H, J=8.5 Hz), 7.62 (d, 4H, J=7.2 Hz), 6.94 (d, 2H, J=4.0 Hz), 6.64 (d, 2H, J=3.5 Hz), 3.22-3.20 (m, 4H), 1.68-1.62 (m, 4H), 1.50-1.44 (m, 4H,) 1.37-1.25 (m, 12H), 0.87 (t, 6H, J=6.5 Hz). .sup.13C NMR (125 MHz, CDCl.sub.3) 159.3, 147.0, 144.4, 139.2, 137.5, 136.2, 129.3, 123.0, 119.8, 116.1, 116.1, 31.8, 30.6, 30.4, 30.1, 29.1, 22.7, 14.1.

(62) ##STR00113##

6,12-diheptyl-3,9-bis(4-(methoxymethyl)phenyl)-5H, 11H-dipyrrolo[1,2-b:1,2-g][2,6]naphthyridine-5,11-dione (9c (A-23))

(63) Prepared from 1-bromo-4-(methoxymethyl)benzene (43.3 mg, 0.25 mmol, 36.0 L). Product was purified using two column chromatographies (SiO.sub.2, dichloromethane). Compound (14.8 mg, 22% yield) was obtained as a dark brown crystals with copper luster. R.sub.f=0.32 (SiO.sub.2, DCM, 1:1). .sup.1H NMR (500 MHz, CDCl.sub.3) 7.47 (d, 4H, J=8.0 Hz), 7.36 (d, 4H, J=8.0 Hz), 6.85 (d, 2H, J=3.5 Hz), 6.50 (d, 2H, J=3.5 Hz), 4.52 (s, 4H), 3.45 (s, 6H), 3.21-3.18 (m, 4H), 1.69-1.63 (m, 4H), 1.49-1.43 (m, 4H) 1.37-1.25 (m, 12H), 0.88 (t, 6H, J=6.5 Hz). .sup.13C NMR (125 MHz, CDCl.sub.3) 159.7, 143.3, 139.8, 137.9, 135.3, 132.3, 128.7, 126.9, 118.2, 115.8, 115.5, 74.5, 58.3, 31.8, 30.5, 30.2, 29.7, 29.2, 22.7, 14.1. HRMS (ESI) calcd for C.sub.44H.sub.53N.sub.2O.sub.4 673.4005 [M+H.sup.+], found 673.3992.

Example 13

Synthesis of Polymer (P-9)

(64) ##STR00114## ##STR00115##

(65) Compound A-16 (100.0 mg, 0.205 mmol), DPP [1224430-28-7] (231.5 mg, 0.205 mmol), pivalic acid (20.1 mg, 0.205 mmol), K.sub.2CO.sub.3 (113.1 mg, 0.818 mmol), Pd(OAc).sub.2 (2.3 mg, 0.01 mmol, 5 mol %) and PCy.sub.3.HBF.sub.4 (7.5 mg, 0.02 mol, 10 mol %) were placed in a Schlenk flask. The vessel was evacuated and backfilled with nitrogen (3 times), and anhydrous, degassed toluene was added via syringe. The Schlenk flask was closed and stirred at 120 C. for 48 h. The reaction mixture was cooled down to room temperature and poured into MeOH (150 mL). After filtration, the obtained solid was subjected to Soxhlet extraction (successively with heptane and toluene). Removing the solvent from the toluene fraction gave a bluish polymer. HT-GPC of the crude polymer: M.sub.n=29,446 Da; M.sub.w=77,720 Da; PD=2.64. The UV-Vis spectra of the polymer was recorded in toluene, which showed a strong absorption in the NIR with .sub.max at 866 nm.

Example 14

Synthesis of Polymer (P-10)

(66) ##STR00116## ##STR00117##

(67) Polymer P10 was made according to the procedure given for polymer P9 from compound A-16 and DPP [1801150-23-1]. M.sub.n=19,717 Da; M.sub.w=58,259 Da; PD=2.96.

Example 15

Synthesis of Polymer (P-11)

(68) ##STR00118## ##STR00119##

(69) Polymer P11 was made according to the procedure given for polymer P9 from compound A-16 and compound 10. Mn=7,265 Da; M.sub.w=15,068 Da; PD=2.07.

Example 16

Synthesis of Polymer (P-12)

(70) ##STR00120## ##STR00121##

(71) Polymer P12 was made according to the procedure given for polymer P9 from compound A-16 and compound 11. M.sub.n=8,577 Da; M.sub.w=21,864 Da; PD=2.55.

Application Example A1

Fabrication and Electrical Characterization of an Organic Field-Effect Transistor (OFET) Based on Polymer P9

(72) Preparation of Back-Contact, Top-Gate FETs

(73) The compound is dissolved at a concentration of 0.75 wt % in chlorobenzene and subsequently spincoated (1200 rpm, 15 s) onto a PET-substrate with lithographically prepatterned gold contacts, serving as Source and Drain contact of the FET. After the coating is completed, the respective substrate is immediately transferred onto a preheated hotplate and heated for 30 s at 90 C. Next the gate dielectric layer consisting of Cytop CTL-809 M is spincoated on top of the organic semiconductor (1200 rpm, 30 s). After pincoating, the substrate is again transferred to the hotplate and annealed for another 30 Min at 90 C. The thickness of the dielectric layer is 620 nm measured by profilometer. Finally 70 nm thick shadow-mask patterned silver gate electrodes are deposited by vacuum evaporation to complete FETs in the BCTG-configuration.

(74) Electrical Characterization

(75) The mobility is calculated from the root representation of the transfer characteristic curve (solid grey curve) in the saturation region. The slope m is determined from the dashed black line in the FIGURE. The dashed black line in the FIGURE is fitted to a region of the square root representation of the Drain current ID such that a good correlation to the linear slope of the root representation is obtained.

(76) The threshold voltage U.sub.Th can be taken from the intersection of black dashed line in the FIGURE with the X-axis portion (V.sub.GS).

(77) In order to calculate the electrical properties of the OFET, the following equations are employed:

(78) $\begin{array}{c}=\frac{m^2*2L}{C_G*W}\end{array}\begin{array}{c}{C}_G={\mathrm{.Math.}}_0*{\mathrm{.Math.}}_r\frac{1}{d}\end{array}\begin{array}{c}{U}_{\mathrm{Th}}=-1*\frac{m}{d}\end{array}$$\begin{array}{c}\frac{\mathrm{ON}}{\mathrm{OFF}}=\frac{I_D\max }{I_D\min }\end{array}$
where .sub.0 is the vacuum permittivity of 8.8510.sup.12 As/Vm. .sub.r=2.1 for Cytop and d is the thickness of the dielectric. The width over length ratio W/L is 25.

(79) The following mobilities, threshold voltage and ON/OFF Ratio have been calculated for the respective polymer from an average of 27 TFTs:

(80) TABLE-US-00004 Field-effect mobility Threshold voltage Compound [cm.sup.2/Vs] U.sub.TH [V] ON/OFF ratio P9 0.013 7.5 2E4