Double donor functionalisation of the peri-positions of perylene and naphthalene monoimide via versatile building blocks

Abstract

The present invention provides the compounds of formulae (3) and (1) wherein n is 0 or 1, R.sup.13 and R.sup.14 are the same or different and are selected from the group consisting of NHR.sup.310, NR.sup.311R.sup.312, OR.sup.313, SR.sup.314 and R.sup.315, or R.sup.13 and R.sup.14 together are selected from the group consisting of (a), (b) and (c), and X is CI, Br of I, and a process for the preparation of compounds of formula (3) comprising the compounds of formula (1) as key intermediates. ##STR00001##

Claims

1. A compound of formula (3) ##STR00075## wherein n is 0 or 1, R.sup.13 and R.sup.14 are the same or different and are selected from the group consisting of NHR.sup.310, NR.sup.311R.sup.312, OR.sup.313, SR.sup.314 and R.sup.315, wherein R.sup.310, R.sup.311, R.sup.312, R.sup.313, R.sup.314 and R.sup.315 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, provided that R.sup.315 does not represent a methyl group, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3010R.sup.3011, OR.sup.3012 and SR.sup.3013, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3014R.sup.3015, OR.sup.3016 and SR.sup.3017, wherein R.sup.3010, R.sup.3011, R.sup.3012, R.sup.3013, R.sup.3014, R.sup.3015, R.sup.3016 and R.sup.3017 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.13 and R.sup.14 together are selected from the group consisting of ##STR00076## wherein L.sup.1 and L.sup.2 are C.sub.1-6-alkylene, C.sub.6-14-arylene, or C.sub.1-6-alkylene-C.sub.6-14-arylene-C.sub.1-6-alkylene, R.sup.25 is H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3030R.sup.3031, OR.sup.3032 and SR.sup.3033, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3034R.sup.3035, OR.sup.3036 and SR.sup.3037, wherein R.sup.3030, R.sup.3031, R.sup.3032, R.sup.3033, R.sup.3034, R.sup.3035, R.sup.3036 and R.sup.3037 are the same or different and are C.sub.1-10-alkyl or phenyl, L.sup.3 is a direct bond, C.sub.1-6-alkylene, C.sub.6-14-arylene, or C.sub.1-6-alkylene-C.sub.6-14-arylene-C.sub.1-6-alkylene, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21 and R.sup.22 are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R.sup.300, OR.sup.301, SR.sup.302, OC(O)R.sup.303, C(O)OR.sup.304 and NR.sup.305R.sup.306, wherein R.sup.300, R.sup.301, R.sup.302, R.sup.303, R.sup.304, R.sup.305 and R.sup.306 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3000R.sup.3001, OR.sup.3002, SR.sup.3003, NO.sub.2, CN and halogen, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3004R.sup.3005, OR.sup.3006, SR.sup.3007, NO.sub.2, CN and halogen, wherein R.sup.3000, R.sup.3001, R.sup.3002, R.sup.3003, R.sup.3004, R.sup.3005, R.sup.3006 and R.sup.3007 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.17 and R.sup.19, respectively, R.sup.18 and R.sup.20 together are ##STR00077## and R.sup.23 and R.sup.24 together are ##STR00078## wherein R.sup.26, R.sup.27 and R.sup.28 are H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, wherein M.sup.1 is H, alkali metal or N(R.sup.3020R.sup.3021R.sup.3022R.sup.3023), wherein R.sup.3020, R.sup.3021, R.sup.3022, and R.sup.3023 are the same or different and are C.sub.1-10-alkyl, or R.sup.27 and R.sup.28 together with the unit ##STR00079## form a five or six membered ring which may be substituted with one or more substituents selected from the group consisting of COOM.sup.2, SO.sub.3M.sup.2, PO.sub.3M.sup.2, NO.sub.2, CN and halogen, wherein M.sup.2 is H, alkali metal or N(R.sup.3024R.sup.3025R.sup.3026R.sup.3027), wherein R.sup.3024, R.sup.3025, R.sup.3026, and R.sup.3027 are the same or different and are C.sub.1-10-alkyl, with the proviso that if n is 1, R.sup.13 and R.sup.14 are phenyl substituted with N(phenyl).sub.2, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.21 and R.sup.22 are H, one of R.sup.19 and R.sup.20 is phenyl substituted with N(phenyl).sub.2, and the other of R.sup.19 and R.sup.20 is H or phenyl substituted with N(phenyl).sub.2, then R.sup.23 and R.sup.24 together are not ##STR00080## wherein R.sup.26 is 2-ethylhexyl.

2. The compound of claim 1, wherein n is 1.

3. The compound of claim 2, wherein R.sup.15, R.sup.16, R.sup.21 and R.sup.22 are H, and R.sup.17, R.sup.18, R.sup.19 and R.sup.20 are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R.sup.300, OR.sup.301, SR.sup.302, OC(O)R.sup.303, C(O)OR.sup.304 and NR.sup.305R.sup.306, wherein R.sup.300, R.sup.301, R.sup.302, R.sup.303, R.sup.304, R.sup.305 and R.sup.306 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3000R.sup.3001, OR.sup.3002, SR.sup.3003, NO.sub.2, CN and halogen, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3004R.sup.3005, OR.sup.3006, SR.sup.3007, NO.sub.2, CN and halogen, wherein R.sup.3000, R.sup.3001, R.sup.3002, R.sup.3003, R.sup.3004, R.sup.3005, R.sup.3006 and R.sup.3007 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.17 and R.sup.19, respectively, R.sup.18 and R.sup.20 together are ##STR00081##

4. The compound of claim 3, wherein R.sup.15, R.sup.16, R.sup.21 and R.sup.22 are H, and R.sup.17, R.sup.18, R.sup.19 and R.sup.20 are the same or different and are H or Cl.

5. The compound of claim 1, wherein R.sup.13 and R.sup.14 are the same or different and are selected from the group consisting of NHR.sup.310, NR.sup.311R.sup.312 and R.sup.315, wherein R.sup.310, R.sup.311, R.sup.312 and R.sup.315 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl or C.sub.6-14-aryl, provided that R.sup.315 does not represent a methyl group, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3010R.sup.3011, OR.sup.3012 and SR.sup.3013, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3014R.sup.3015, OR.sup.3016 and SR.sup.3017, wherein R.sup.3010, R.sup.3011, R.sup.3012, R.sup.3013, R.sup.3014, R.sup.3015, R.sup.3016 and R.sup.3017 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.13 and R.sup.14 together are selected from the group consisting of ##STR00082## wherein L.sup.2 is C.sub.1-6-alkylene, C.sub.6-14-arylene, or C.sub.1-6-alkylene-C.sub.6-14-arylene-C.sub.1-6-alkylene, R.sup.25 is H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3030R.sup.3031, OR.sup.3032 and SR.sup.3033, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3034R.sup.3035, OR.sup.3036 and SR.sup.3037, wherein R.sup.3030, R.sup.3031, R.sup.3032, R.sup.3033, R.sup.3034, R.sup.3035, R.sup.3036 and R.sup.3037 are the same or different and are C.sub.1-10-alkyl or phenyl.

6. The compound of claim 1, wherein R.sup.13 and R.sup.14 are the same or different and are selected from the group consisting of NHR.sup.310 and R.sup.315, wherein R.sup.310 and R.sup.315 are C.sub.6-14-aryl, wherein C.sub.6-14-aryl may be substituted with NR.sup.3014R.sup.3015, wherein R.sup.3014 and R.sup.3015 are phenyl, or R.sup.13 and R.sup.14 together are ##STR00083## wherein L.sup.2 is C.sub.1-6-alkylene or C.sub.6-14-arylene, R.sup.25 is H or C.sub.6-14-aryl.

7. The compound of claim 1, wherein R.sup.23 and R.sup.24 together are ##STR00084## wherein R.sup.26, R.sup.27 and R.sup.28 are C.sub.1-20-alkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl may be substituted with one or more substituents selected from the group consisting of phenyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, wherein M.sup.1 is H, alkali metal or N(R.sup.3020R.sup.3021R.sup.3022R.sup.3023), wherein R.sup.3020, R.sup.3021, R.sup.3022, and R.sup.3023 are the same or different and are C.sub.1-10-alkyl, or R.sup.27 and R.sup.28 together with the unit ##STR00085## form a five or six membered ring which may be substituted with one or more substituents selected from the group consisting of COOM.sup.2, SO.sub.3M.sup.2, PO.sub.3M.sup.2, NO.sub.2, CN and halogen, wherein M.sup.2 is H, alkali metal or N(R.sup.3024R.sup.3025R.sup.3026R.sup.3027), wherein R.sup.3024, R.sup.3025, R.sup.3026, and R.sup.3027 are the same or different and are C.sub.1-10-alkyl.

8. The compound of claim 1, wherein R.sup.23 and R.sup.24 together are ##STR00086## wherein R.sup.26, R.sup.27 and R.sup.28 are C.sub.1-20-alkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl may be substituted with COOM.sup.1, wherein M.sup.1 is H, or R.sup.27 and R.sup.28 together with the unit ##STR00087## form a five membered ring which may be substituted with one or more substituents selected from the group consisting of COOM.sup.2 and CN, wherein M.sup.2 is H.

9. A process for the preparation of a compound of formula (3) according to claim 1, ##STR00088## ##STR00089## ##STR00090## ##STR00091## the process comprising treating a compound of formula (2) ##STR00092## wherein n has the meaning as depicted for formula (3), R.sup.9 and R.sup.10 are the same or different and are COOH or COOR.sup.29, wherein R.sup.29 is C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.2010R.sup.2011, OR.sup.2012 and SR.sup.2013, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.2014R.sup.2015, OR.sup.2016 and SR.sup.2017, wherein R.sup.2010, R.sup.2011, R.sup.2012 and R.sup.2013, R.sup.2014, R.sup.2015, R.sup.2016 and R.sup.2017 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.9 and R.sup.10 together are ##STR00093## R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R.sup.200, OR.sup.201, SR.sup.202, OC(O)R.sup.203, C(O)OR.sup.204 or NR.sup.205R.sup.206, wherein R.sup.200, R.sup.201, R.sup.202, R.sup.203, R.sup.204, R.sup.205 and R.sup.206 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.2000R.sup.2001, OR.sup.2002, SR.sup.2003, NO.sub.2, CN and halogen, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.2004R.sup.2005, OR.sup.2006, SR.sup.2007, NO.sub.2, CN and halogen, wherein R.sup.2000, R.sup.2001, R.sup.2002, R.sup.2003, R.sup.2004, R.sup.2005, R.sup.2006 and R.sup.2007 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.3 and R.sup.5, respectively, R.sup.4 and R.sup.6 together are ##STR00094## and R.sup.11 and R.sup.12 together are ##STR00095## wherein R.sup.30 is C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl or heteroaryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NO.sub.2, CN and halogen, and C.sub.6-14-aryl and heteroaryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NO.sub.2, CN and halogen, with a) M.sup.3OH, wherein M.sup.3 is an alkali metal, N(R.sup.400R.sup.401R.sup.402R.sup.403), P(R.sup.400R.sup.401R.sup.402R.sup.403) or guanidinium, wherein R.sup.400, R.sup.401, R.sup.402 and R.sup.403 are the same or different and are selected from the group consisting of H, C.sub.1-20-alkyl and C.sub.6-14-aryl, wherein C.sub.1-20-alkyl may be substituted with phenyl, and C.sub.6-14-aryl may be substituted with C.sub.1-10-alkyl, b) an acid and c) an X-donor, wherein X is Cl, Br or I, in order to obtain a compound of formula (1) ##STR00096## wherein n has the meaning as depicted for formula (3), X has the meaning as depicted for the X-donor, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.11 and R.sup.12 have the meaning as depicted for formula (2).

10. The process of claim 9, wherein R.sup.9 and R.sup.10 together are ##STR00097##

11. The process of claim 9, wherein R.sup.11 and R.sup.12 together are ##STR00098##

12. The process of claim 9, wherein n is 1.

13. The process of claim 12, wherein R.sup.1, R.sup.2, R.sup.7 and R.sup.8 are H, and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R.sup.200, OR.sup.201, SR.sup.202, OC(O)R.sup.203, C(O)OR.sup.204 or NR.sup.205R.sup.206, wherein R.sup.200, R.sup.201, R.sup.202, R.sup.203, R.sup.204, R.sup.205 and R.sup.206 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.2000R.sup.2001, OR.sup.2002, SR.sup.2003, NO.sub.2, CN and halogen, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.2004R.sup.2005, OR.sup.2006, SR.sup.2007, NO.sub.2, CN and halogen, wherein R.sup.2000, R.sup.2001, R.sup.2002, R.sup.2003, R.sup.2004, R.sup.2005, R.sup.2006 and R.sup.2007 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.3 and R.sup.5, respectively, R.sup.4 and R.sup.6 together are ##STR00099## and R.sup.15, R.sup.16, R.sup.21 and R.sup.22 are H, and R.sup.17, R.sup.18, R.sup.19 and R.sup.20 are the same or different and are selected from the group consisting of H, F, Cl, Br, I, CN, R.sup.300, OR.sup.301, SR.sup.302, OC(O)R.sup.303, C(O)OR.sup.304 and NR.sup.305R.sup.306, wherein R.sup.300, R.sup.301, R.sup.302, R.sup.303, R.sup.304, R.sup.305 and R.sup.306 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3000R.sup.3001, OR.sup.3002, SR.sup.3003, NO.sub.2, CN and halogen, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3004R.sup.3005, OR.sup.3006, SR.sup.3007, NO.sub.2, CN and halogen, wherein R.sup.3000, R.sup.3001, R.sup.3002, R.sup.3003, R.sup.3004, R.sup.3005, R.sup.3006 and R.sup.3007 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.17 and R.sup.19, respectively, R.sup.18 and R.sup.20 together are ##STR00100##

14. The process of claim 13, wherein R.sup.1, R.sup.2, R.sup.7 and R.sup.8 are H, and R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are the same or different and are H or Cl, and R.sup.15, R.sup.16, R.sup.21 and R.sup.22 are H, and R.sup.17, R.sup.18, R.sup.19 and R.sup.20 are the same or different and are H or Cl.

15. The process of claim 9, wherein R.sup.13 and R.sup.14 are the same and are selected from the group consisting of NHR.sup.310, NR.sup.311R.sup.312 and R.sup.315, wherein R.sup.310, R.sup.311, R.sup.312 and R.sup.315 are C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3010R.sup.3011, OR.sup.3012 and SR.sup.3013, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3014R.sup.3015, OR.sup.3016 and SR.sup.3017, wherein R.sup.3010, R.sup.3011, R.sup.3012, R.sup.3013, R.sup.3014, R.sup.3015, R.sup.3016 and R.sup.3017 are the same or different and are C.sub.1-10-alkyl or phenyl, or R.sup.13 and R.sup.14 together are ##STR00101## wherein L.sup.2 is C.sub.1-6-alkylene, C.sub.6-14-arylene, or C.sub.1-6-alkylene-C.sub.6-14-arylene-C.sub.1-6-alkylene, R.sup.25 is H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl and C.sub.5-8-cycloalkyl may be substituted with one or more substituents selected from the group consisting of phenyl, NR.sup.3030R.sup.3031, OR.sup.3032 and SR.sup.3033, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, NR.sup.3034R.sup.3035, OR.sup.3036 and SR.sup.3037, wherein R.sup.3030, R.sup.3031, R.sup.3032, R.sup.3033, R.sup.3034, R.sup.3035, R.sup.3036 and R.sup.3037 are the same or different and are C.sub.1-10-alkyl or phenyl.

16. The process of claim 9, wherein R.sup.13 and R.sup.14 are the same and are selected from the group consisting of NHR.sup.310 and R.sup.315, wherein R.sup.310 and R.sup.315 are C.sub.6-14-aryl, wherein C.sub.6-14-aryl may be substituted with NR.sup.3014R.sup.3015, wherein R.sup.3014 and R.sup.3015 are phenyl, or R.sup.13 and R.sup.14 together are ##STR00102## wherein L.sup.2 is C.sub.1-6-alkylene or C.sub.6-14-arylene, R.sup.25 is H or C.sub.6-14-aryl.

17. The process of claim 9, wherein R.sup.23 and R.sup.24 together are ##STR00103## wherein R.sup.26, R.sup.27 and R.sup.28 are C.sub.1-20-alkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl may be substituted with one or more substituents selected from the group consisting of phenyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, and C.sub.6-14-aryl may be substituted with one or more substituents selected from the group consisting of C.sub.1-10-alkyl, COOM.sup.1, SO.sub.3M.sup.1, PO.sub.3M.sup.1, NO.sub.2, CN and halogen, wherein M.sup.1 is H, alkali metal or N(R.sup.3020R.sup.3021R.sup.3022R.sup.3023), wherein R.sup.3020, R.sup.3021, R.sup.3022, and R.sup.3023 are the same or different and are C.sub.1-10-alkyl, or R.sup.27 and R.sup.28 together with the unit ##STR00104## form a five or six membered ring which may be substituted with one or more substituents selected from the group consisting of COOM.sup.2, SO.sub.3M.sup.2, PO.sub.3M.sup.2, NO.sub.2, CN and halogen, wherein M.sup.2 is H, alkali metal or N(R.sup.3024R.sup.3025R.sup.3026R.sup.3027), wherein R.sup.3024, R.sup.3025, R.sup.3026, and R.sup.3027 are the same or different and are C.sub.1-10-alkyl.

18. The process of claim 9, wherein R.sup.23 and R.sup.24 together are ##STR00105## wherein R.sup.26, R.sup.27 and R.sup.28 are C.sub.1-20-alkyl or C.sub.6-14-aryl, wherein C.sub.1-20-alkyl may be substituted with COOM.sup.1, wherein M.sup.1 is H, or R.sup.27 and R.sup.28 together with the unit ##STR00106## form a five membered ring which may be substituted with one or more substituents selected from the group consisting of COOM.sup.2 and CN, wherein M.sup.2 is H.

Description

(1) FIG. 1 shows the absorbance of the compounds of formulae 3a, 3b, 3c, 3d and 3e in dichloromethane against the wavelength in the range of 350 to 800 nm.

(2) FIG. 2 shows the absorbance of the device of example 14 comprising the compound of formula 3e, before the fabrication of the solid-state dye-sensitized solar cell (ssDSC) was completed by evaporation of 200 nm of silver as the counter electrode, against the wavelength.

(3) FIG. 3 shows the current density I against the voltage of the solid-state dye-sensitized solar cell (sDSC) of example 14 comprising the compound of formula 3e.

(4) FIG. 4 shows the external quantum efficieny EQE against the wavelength of the solid-state dye-sensitized solar cell (ssDSC) of example 14 comprising the compound of formula 3e.

(5) FIG. 5 shows the absorbance of the device of example 15 comprising the compound of formula 3i, before the fabrication of the solid-state dye-sensitized solar cell (ssDSC) was completed by evaporation of 200 nm of silver as the counter electrode, against the wavelength.

(6) FIG. 6 shows the current density I against the voltage of the solid-state dye-sensitized solar cell (ssDSC) of example 15 comprising the compound of formula 3i.

(7) FIG. 7 shows the external quantum efficieny EQE against the wavelength [nm] of the solid-state dye-sensitized solar cell (ssDSC) of example 15 comprising the compound of formula 3i.

EXAMPLES

Example 1

Preparation of Compound 1a

(8) ##STR00063##

(9) 30 ml 1M NaOH was added to a suspension of compound 2a (2.65 g, 5.00 mmol) in 100 ml water and the mixture was stirred to obtain a limpid solution. The mixture was heated (80 C.) and 30 mmol acetic acid was added. Bromine (11 mmol, 0.57 ml) was added in one portion and the reaction mixture was stirred at 80 C. for 2 h. The precipitate was filtered, washed with water and dried. The solid was suspended in 50 ml methanol and 50 ml acetic acid and stirred for 5 h at 100 C. The mixture was poured in methanol (200 ml) and precipitate was filtered, washed with methanol and dried. Yield 2.65 g (86%). FD mass spectrum (8 kV): m/z (%): calcd for 617.89. found: 616.8. .sup.1H NMR (300 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 8.20 (s, 2H); 8.63 (s, 2H). Elemental analysis calcd (%) for C.sub.22H.sub.4Br.sub.2C.sub.14N.sub.3O.sub.3: C, 42.76; H, 0.65. found: C, 42.76; H, 0.66.

Example 2

Preparation of Compound 3a

(10) ##STR00064##

(11) A suspension of compound 1a (0.64 g, 2.0 mmol) in 8 ml aniline was stirred at 180 C. under argon for 5 h. The mixture was poured into 10% hydrochloric acid and ice. The precipitate was filtered, washed with water and water/methanol 1:1. Crude compound 3a was purified by column chromatography using dichloromethane as eluent on silica. Yield 1.01 g (70%). .sup.1H NMR (300 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 7.17-7.22 (m, 6H); 7.33-7.35 (m, 2H); 7.34 (s, 2H); 7.40-7.46 (m, 4H); 7.52-7.63 (m, 3H); 7.86 (s, 2H, NH) 8.56 (s, 2H). .sup.13C NMR (75.0 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 113.86 (1C); 116.13 (2C); 116.85 (2C); 119.37 (2C); 121.15 (4C); 123.61 (1C); 124.53 (2C); 128.76 (1C); 129.37 (2C); 129.90 (4C); 130.64 (2C); 131.64 (2C); 131.83 (1C); 132.55 (2C); 135.04 (1C); 135.86 (1C); 137.75 (2C); 140.53 (2C); 145.27 (2C); 163.07 (2C, CO). FD mass spectrum (8 kV): m/z (%): calcd for 717.43. found: 715.7 (100) [M].sup.+. Elemental analysis calcd (%) for C.sub.40H.sub.21CL.sub.4N.sub.3O.sub.2: C, 66.97; H, 2.95; N, 5.86. found: C, 66.41; H, 3.08; N, 5.86. UV-Vis (CH.sub.2Cl.sub.2): .sub.max=615 (33 163) nm (M.sup.1 cm.sup.1).

Example 3

Preparation of Compound 3b

(12) ##STR00065##

(13) 0.10 ml trifluoroacetic acid was added to a solution of compound 3a (0.72 g, 1.00 mmol) and paraformaldehyde (0.120 g, 4.0 mmol) in 100 ml chloroform and the reaction mixture was refluxed for 1.5 h under argon. The solvent was removed under vacuum and the crude solid was purified by column chromatography using dichloromethane as eluent on silica. Yield 0.70 g (96%). .sup.1H NMR (300 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 5.38 (s, 2H, CH.sub.2); 6.91 (s, 2H); 7.33-7.45 (m, 8H); 7.53-7.62 (m, 7H); 8.56 (s, 2H). .sup.13C NMR (75.0 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 67.21 (1C, CH.sub.2); 109.65 ((1C)); 109.87 ((2C)); 114.44 ((2C)); 118.65 ((2C)); 124.09 ((1C)); 124.75 ((4C)); 127.33 ((2C)); 128.68 ((2C)); 129.34 ((2C)); 129.52 ((2C)); 130.32 ((4C)); 131.77 ((2C)); 131.87 ((1C)); 132.55 ((1C)); 133.98 ((1C)); 135.20 ((1C)); 138.45 ((2C)); 142.02 ((2C)); 144.59 ((2C)); 163.15 ((2C), CO). FD mass spectrum (8 kV): m/z (%): calcd for 729.44. found: 729.5 (100) [M].sup.+. Elemental analysis calcd (%) for C.sub.41H.sub.21O.sub.4N.sub.3O.sub.2: C, 67.51; H, 2.90; N, 5.76. found: C, 67.44; H, 2.83; N, 5.79. UV-Vis (CH.sub.2Cl.sub.2): .sub.max=635 (45 092) nm (M.sup.1 cm.sup.1).

Example 4

Preparation of Compound 3c

(14) ##STR00066##

(15) A mixture of potassium hydroxide (3.0 g) and compound 3b (0.68 g, 1.08 mmol) in 30 ml 1,2-ethanediol was stirred an heated at 165 C. for 4 h. The mixture was cooled and diluted with 50 ml 10% hydrochloric acid. The precipitate was filtered, washed with water and dried. The crude solid was purified by column chromatography using dichloromethane/acetone as eluent on silica. Yield 0.40 g (63%). .sup.1H NMR (300 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 5.37 (s, 2H, CH.sub.2); 6.87 (d, 2H, .sup.3J.sub.HH=8.6 Hz); 7.25-7.39 (m, 8H); 7.45-7.55 (m, 7H); 7.83 (d, 2H, .sup.3J.sub.HH=8.5 Hz); 8.11 (d, 2H, .sup.3J.sub.HH=8.9 Hz); 8.29 (d, 2H, .sup.3J.sub.HH=8.2 Hz). .sup.13C NMR (75.0 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 67.06 (1C, CH.sub.2); 108.56 (2C); 114.10 (1C); 116.55 (1C); 116.77 (2C); 119.34 (2C); 124.60 (4C); 125.75 (1C); 126.31 (2C); 126.92 (2C); 128.13 (1C); 128.70 (2C); 128.84 (2C); 129.06 (2C); 129.94 (4C); 130.90 (1C); 131.32 (2C); 136.00 (1C); 138.66 (2C); 143.04 (2C); 144.83 (2C); 163.99 (2C, CO). FD mass spectrum (8 kV): m/z (%): calcd for 591.66. found: 591.9 (100) [M].sup.+. UV-Vis (CH.sub.2Cl.sub.2): .sub.max=655 (45 398) nm (M.sup.1 cm.sup.1).

Example 5

Preparation of Compound 3d

(16) ##STR00067##

(17) Potassium hydroxide (1.0 g) was added to a solution of compound 3c (0.30 g, 0.51 mmol) in tert-buthanol (30 ml) and 1,4-dioxane (10 ml), and the reaction mixture was refluxed overnight under argon. The mixture was poured into 10% hydrochloric acid and ice. The precipitate was filtered, washed with water and water/methanol 1:1. The crude product was dissolved in THF/AcOH (5:1) and reflux for 5 h. The solvent was removed under reduced pressure and crude compound 3d was used without further purification Yield 0.25 g (95%). FD mass spectrum (8 kV): m/z (%): calcd for 516.54. found: 516.3 (100) [M].sup.+.

Example 6

Preparation of Compound 3e

(18) ##STR00068##

(19) A mixture of compound 3d (0.25 g, 0.48 mmol), glycine (0.20 g) and imidazole (2.0 g) was stirred at 140 C. under argon atmosphere for 4 h. The mixture was poured into 10% hydrochloric acid and ice. The precipitate was filtered, washed with water and water/methanol 1:1. Crude compound 3e was dissolved in THF and precipitated in water/methanol 1:2. Yield 0.24 g (87%). .sup.1H NMR (300 MHz, DMSO-d.sub.6, 300K): 4.65 (s, 2H, CH.sub.2COOH); 5.38 (s, 2H, NCH.sub.2N); 6.78 (d, 2H, .sup.3J.sub.HH=8.6 Hz); 7.27-7.35 (m, 2H); 7.45-7.56 (m, 8H); 7.92 (d, 2H, .sup.3J.sub.HH=8.5 Hz); 8.04 (d, 2H, .sup.3J.sub.HH=8.3 Hz); 8.25 (d, 2H, .sup.3J.sub.HH=8.9 Hz); 12.93 (bs, 1H, COOH). .sup.13C NMR (75.0 MHz, DMSO-d.sub.6, 300K): 40.88 (1C, CH.sub.2COOH); 66.81 (10, NCH.sub.2N); 108.62 (2C); 113.78 (1C); 115.73 (2C); 116.85 (1C); 118.82 (2C); 124.24 (4C); 125.09 (1C); 125.95 (2C); 127.72 (2C); 128.27 (1C); 129.86 (4C); 129.94 (2C); 130.86 (2C); 138.19 (2C); 143.01 (2C); 144.58 (2C); 162.50 (2C, CO); 169.66 (1C, COOH). FD mass spectrum (8 kV): m/z (%): calcd for 573.60. found: 573.6 (100) [M].sup.+. UV-Vis (CH.sub.2Cl.sub.2): .sub.max=667 (25 505) nm (M.sup.1 cm.sup.1).

Example 7

Preparation of Compound 1b

(20) ##STR00069##

(21) Pentadecan-8-amine (4.0 mmol, 0.91 g) was added to a suspension of compound 1a (2.0 mmol, 1.24 g) in 20 ml NMP and 10 ml acetic acid. The reaction mixture was stirred at 110 C. for 15 h. After cooling down to room temperature the reaction mixture was poured in water. The precipitate was filtered, washed with methanol, dried and purified by column chromatography using hexane/dichloromethane as eluent on silica. (0.80 g, 48%). FD-Mass: calc.: 827.30. found: 829.3. .sup.1H-NMR ( (ppm), CDCl.sub.3): 0.84 (t, 6H, CH.sub.3, .sup.3J.sub.HH=7.3 Hz); 1.78-1.92 (m, 2H, CH.sub.2); 2.07-2.22 (m, 2H, CH.sub.2); 4.89-4.99 (m, 1H, CHN); 8.08 (s, 2H, H-8 and 11); 8.49 (s, 2H, H-2 and 5).

Example 8

Preparation of Compound 3f

(22) ##STR00070##

(23) A mixture of compound 1 b (0.415 g, 0.5 mmol), and 1,2-diaminobenzene (0.22 g, 2.0 mmol) in 10 ml NMP was stirred at 180 C. under argon for 5 h. The mixture was poured into 10% hydrochloric acid and ice. The precipitate was filtered, washed with water and methanol. Crude compound 3f was purified by column chromatography using dichloromethane as eluent on silica. Yield 0.17 g (43%). .sup.1H NMR (300 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 0.84 (t, 6H, CH.sub.3, .sup.3J.sub.HH=5.9 Hz); 1.14-1.36 (m, 20H, CH.sub.2); 1.80-1.91 (m, 2H, CH.sub.2); 2.15-2.27 (m, 2H, CH.sub.2); 5.09-5.21 (m, 1H, CHN); 6.34 (s, 2H, NH); 6.88 (s, 1H); 6.90 (s, 1H); 6.97-7.07 (m, 4H); 8.50 (s, 1H) 8.53 (s, 1H). .sup.13C NMR (75.0 MHz, C.sub.2D.sub.2Cl.sub.4, 300K): 14.07 (2C CH.sub.3); 22.53 (2C, CH.sub.2); 26.86 (2C, CH.sub.2); 29.09 (2C, CH.sub.2); 29.43 (2C, CH.sub.2); 31.71 (2C, CH.sub.2); 32.21 (2C, CH.sub.2); 54.63 (1C, CHN); 109.07; 116.12; 116.20; 119.83; 123.27; 123.99; 130.50; 130.69; 130.92; 132.18; 132.84; 135.86; 136.75; 143.73; 162.92 (1C, CO); 164.05 (1C, CO). FD-Mass: calc.: 773.62. found: 772.7. UV-Vis (CH.sub.2Cl.sub.2): .sub.max=588 (36 654) nm (M.sup.1 cm.sup.1).

Example 9

Preparation of Compound 1C

(24) ##STR00071##

(25) 20 ml (20 mmol) 1M NaOH was added to a suspension of compound 2b (4.00 mmol) in 20 ml water and the mixture was stirred to obtain a limpid solution. The mixture was heated (90-95 C.) and 20 mmol acetic acid was added. Bromine (0.5 ml, 1.56 g, 10 mmol, 2.5 equiv) was added in one portion and the reaction mixture was stirred at 90-95 C. for 24 h. The precipitate was filtered, washed with acetone and dried. Yield 1.35 g (95%). Purity >85%.

Example 10

Preparation of Compound 3g

(26) ##STR00072##

(27) Pd[P(Ph).sub.3].sub.4 (3 mol %) was added to a mixture of compound 1c (2.00 mmol), 4-(diphenylamino)phenylboronic acid (3.5 mmol), 10 ml 1M K.sub.2CO.sub.3 (10.0 mmol) in 50 ml 1,4-dioxane under argon atmosphere. The mixture was stirred at 95 C. under argon atmosphere for 6 h. The solvent was removed under reduced pressure. The solid was dissolved in acetic acid and dichloromethane and reflux overnight. The solvent was removed under reduced pressure. Crude compound 3g was purified by column chromatography using dichloromethane as eluent on silica. Yield 1.065 g (78%). FD-Mass: calc.: 684.78. found: 683.1. .sup.1H-NMR ( (ppm), CD.sub.2Cl.sub.2): 6.75-6.78 (m, 4H); 6.82-6.85 (m, 4H); 6.96-7.02 (m, 4H); 7.05-7.08 (m, 8H); 7.15-7.20 (m, 8H); 7.78 (d, 2H, .sup.3J.sub.HH=7.7 Hz); 8.56 (d, 2H, .sup.3J.sub.HH=7.7 Hz). .sup.13C-NMR ( (ppm), CD.sub.2Cl.sub.2): 117.63 (2C); 121.11 (4C); 124.28 (4C); 125.95 (8C); 128.71 (1C); 130.00 (8C); 131.12 (4C); 131.64 (2C); 133.12 (2C); 133.58 (1C); 134.79 (2C); 147.75 (4C); 147.91 (2C); 149.91 (2C); 161.67 (2C, CO).

Example 11

Preparation of Compound 3h

(28) ##STR00073##

(29) A mixture of compound 3g (0.60 g, 0.88 mmol), 2,3-diaminomaleonitrile (0.38 g, 3.5 mmol), CaO (20 eq) in 20 ml pyridine was stirred and reflux under argon atmosphere for 24 h. The solvent was removed under reduced pressure. Crude compound 3h was purified by column chromatography using hexane/dichloromethane as eluent on silica. Yield 0.130 g (24%). .sup.1H-NMR ( (ppm), CDCl.sub.3): 6.78-6.89 (m, 8H); 6.98-7.03 (m, 4H); 7.08-7.10 (m, 8H); 7.15-7.21 (m, 8H); 7.74 (d, 1H, .sup.3J.sub.HH=7.8 Hz); 7.79 (d, 1H, .sup.3J.sub.HH=7.8 Hz); 8.72 (d, 1H, .sup.3J.sub.HH=7.8 Hz); 8.81 (d, 1H, .sup.3J.sub.HH=7.8 Hz). .sup.13C-NMR ( (ppm), CDCl.sub.3): 107.72; 108.24; 111.42; 116.43; 118.71; 120.51; 120.67; 124.00; 124.14; 125.60; 125.70; 126.93; 128.70; 128.76; 129.23; 129.64; 129.66; 130.89; 131.01; 131.56; 131.60; 134.05; 134.29; 147.09; 147.20; 147.49; 147.87; 148.54; 149.15; 152.38; 157.97.

Example 12

Preparation of compound 3i

(30) ##STR00074##

(31) NaOH (1.0 g) in 3 ml of water was added to a solution of compound 3h (130 mg, 0.17 mmol) in 1,4-dioxane (15 ml). The reaction mixture was stirred at 70 C. overnight. The reaction mixture was cooled down to room temperature and poured into diluted HCl. The precipitate was filtered, washed and dried. Crude compound 3i was purified by recrystallization of methanol. Yield 0.10 g (74%). .sup.1H-NMR ( (ppm), DMSO-d.sub.6): 6.75-6.78 (m, 4H); 6.99-7.13 (m, 16H); 7.27-7.33 (m, 8H); 7.89 (d, 1H, .sup.3J.sub.HH=7.9 Hz); 7.92 (d, 1H, .sup.3J.sub.HH=7.9 Hz); 8.12 (s, 1H, COOH); 8.74 (d, 1H, .sup.3J.sub.HH=7.7 Hz); 8.80 (d, 1H, .sup.3J.sub.HH=7.8 Hz). .sup.13C-NMR ( (ppm), DMSO-d.sub.6): 101.27; 110.75; 117.78; 120.06; 120.12; 120.24; 123.77; 123.89; 124.75; 124.87; 126.96; 127.78; 128.32; 129.61; 130.72; 130.85; 131.30; 132.48; 134.27; 134.58; 145.61; 146.23; 146.57; 146.65; 147.20; 147.36; 149.49; 158.69; 161.07.

Example 13

(32) The absorbance of the compounds of formulae 3a, 3b, 3c, 3d and 3e in dichloromethane were measured in the wavelength range of 350 to 800 nm. The results are shown in FIG. 1.

Example 14

Preparation of Solid-State Dyesensitized Solar Cells (ssDSCs) Comprising the Compound of Formula (3e) as Dye

(33) A TiO.sub.2 blocking layer was prepared on a fluorine-doped tin oxide (FTO)-covered glass substrate using spray pyrolysis (Peng, B.; Jungmann, G.; Jager, C.; Haarer, D.; Schmidt, H. W.; Thelakkat, M. Coord. Chem. Rev. 2004, 248, 1479). Then, a TiO.sub.2 paste (Dyesol), diluted with terpineol, was applied by screen printing, resulting in a film thickness of 1.7 m. All films were then sintered for 45 min at 450 C., followed by treatment in a 40 mM aqueous solution of TiCla at 60 C. for 30 min, followed by another sintering step. The so obtained FTO-covered glass substrates with TiO.sub.2 layers were pretreated with 5 mM solutions of the 2-(p-butoxyphenyl)acetohydroxamic acid sodium salt in ethanol (2-(p-butoxyphenyl)acetohydroxamic acid sodium salt is described on page 52 of WO 2012/001628 A1 as Example No. 6), followed by dyeing in a 0.5 mM solution of a compound of formula (3e) in CH.sub.2Cl.sub.2. Then, 2,2,7,7-tetrakis-(N,N-di-p-methoxyphenyl amine)-9,9-spirobifluorene (Spiro-MeOTAD) was applied by spin-coating from a solution in CH.sub.2Cl.sub.2 (200 mg/mL) also containing 20 mM Li(CF.sub.3SO.sub.2).sub.2N. Fabrication of the ssDSCs was completed by evaporation of 200 nm of silver as the counter electrode. The active area of the ssDSCs was defined by the size of these contacts (0.13 cm.sup.2), and the ssDSC was masked by an aperture of the same area for measurements.

Example 15

Preparation of a Solid-State Dyesensitized Solar Cell (ssDSC) Comprising the Compound of Formula (3i) as Dye

(34) A solid-state dyesensitized solar cell (ssDSC) comprising the compound of formula (3i) as dye was prepared in analogy to example 14.

Example 16

(35) The absorbance of the devices of examples 14 and 15, both before the fabrication of the ssDSCs was completed by evaporation of 200 nm of silver as the counter electrode, against the wavelength were measured.

(36) The plot of the absorbance of the device of examples 14, comprising the compound of formula 3e, before the fabrication of the ssDSCs was completed by evaporation of 200 nm of silver as the counter electrode, against the wavelength is shown in FIG. 2.

(37) The plot of the absorbance of the device of examples 15 comprising the compound of formula 3i, before the fabrication of the ssDSC was completed by evaporation of 200 nm of silver as the counter electrode, against the wavelength is shown in FIG. 5.

Example 17

(38) The current-voltage characteristics for the ssDSCs of examples 14 and 15 were measured with a Keithley 2400 under 1000 W/m.sup.2, AM 1.5G conditions (LOT ORIEL 450 W).

(39) The plots of the current density I against the voltage of the ssDSC of example 14 is shown in FIG. 3.

(40) The plot of the current density I against the voltage of the ssDSC of example 15 is shown in FIG. 6.

(41) The short circuit current Isc, the open circuit voltage Voc, the power conversion efficiency ETA, and the fill factor FF of the ssDCSs of examples 14 and 15 were determined.

(42) The short circuit Isc is I at V=0.

(43) The open circuit Voc is V at I=0.

(44) The fill factor FF is (I.sub.mppV.sub.mpp)/(I.sub.SCV.sub.OC), wherein mpp is the maximum power point.

(45) The power conversion efficiency ETA is the percentage of the solar energy to which the cell is exposed that is converted into electrical energy.

(46) The results are shown in table 1.

(47) TABLE-US-00001 TABLE 1 I.sub.SC V.sub.OC FF ETA Sun ssDCS compound [mA/cm.sup.2] [mV] [%] [%] [mW/cm.sup.2] Ex 14 3e 2.51 700 66 1.2 100.00 Ex. 15 3i 4.99 780 61 2.4 100.00

Example 18

(48) The external quantum efficiency EQE was obtained with an Acton Research Monochromator using additional white background light illumination.

(49) The external quantum efficiency EQE is the ratio of the number of charge carriers collected by the solar cell to the number of photons of a given energy shining on the solar cell from outside (incident photons).

(50) The plots of the external quantum efficiency EQE against the wavelength of the ssDSC of example 14 is shown in FIG. 4.

(51) The plot of the external quantum efficiency EQE against the wavelength [nm] of the ssDSC of example 15 is shown in FIG. 7.