Organic dyes comprising a hydrazone moiety and their use in dye-sensitized solar cells

Abstract

The present invention relates to compounds of general formula I ##STR00001##
wherein R.sup.100 and R.sup.200 are each independently hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl or aryloxy-C.sub.1-C.sub.10-alkyl, D is an m-valent (m=1, 2 or 3) donor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, A is an acceptor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, and the donor moiety D and the acceptor moiety A are π-conjugated to one another. Furthermore, the present invention relates to the use of compounds of formula I for producing dye-sensitized solar cells and to dye-sensitized solar cells comprising compounds of formula I.

Claims

1. A compound represented by formula (I): ##STR00066## wherein R.sup.100 and R.sup.200 are each independently hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl or aryloxy-C.sub.1-C.sub.10-alkyl, D is an m-valent donor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, A is an acceptor moiety which comprises at least one carbon-carbon or carbon-heteroatom double bond and/or at least one unfused or fused carbo- or heterocyclic ring, m is 1, 2 or 3, the donor moiety D and the acceptor moiety A are π-conjugated to one another, when m=1 the donor moiety D is selected from the group consisting of: ##STR00067## ##STR00068## R.sup.110, R.sup.120 and R.sup.130 independently hydrogen, halogen, hydroxyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-alkylamino, di(C.sub.1-C.sub.10-alkyl)amino, C.sub.1-C.sub.10-alkylamino- or di(C.sub.1-C.sub.10-alkyl)aminosulfonylamino, C.sub.1-C.sub.10-alkylsulfonylamino, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or an —NHCOR.sup.170 or —NHCOOR.sup.170 radical, R.sup.140, R.sup.150 and R.sup.160 are each independently hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or in case R.sup.140 and R.sup.160 or R.sup.150 and R.sup.160 are bonded to adjacent carbon atoms these pairs of groups may—together with the carbon atoms to which they are bonded—form a five- or six-membered ring in which one CH.sub.2 group may be replaced by an oxygen atom, R.sup.170 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms and in case of two moities for m=2 may vary independently of each other, R.sup.210, R.sup.220, R.sup.230 and R.sup.240 are each independently aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.10-cycloalkyl, or R.sup.210 and R.sup.220 and/or R.sup.230 and R.sup.240 form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR.sup.210R.sup.220 and R.sup.110 are bonded to adjacent carbon atoms, R.sup.110 and R.sup.210 or R.sup.110 and R.sup.220—together with the nitrogen atom of the moiety NR.sup.210R.sup.220 and the carbon atom to which the moieties NR.sup.210R.sup.220 and R.sup.110 are bonded—form a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring, R.sup.250 and R.sup.260 are each independently C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl or aryloxy-C.sub.1-C.sub.10-alkyl, Z is O or S, when m=2 the donor moiety D is selected from the group consisting of: ##STR00069## wherein R.sup.170 is defined above and in case of two moieties may vary independently of each other, when m=3 the donor moiety D is selected from the group consisting of: ##STR00070## wherein R.sup.170 is defined above, A is represented by formula (Ia): ##STR00071## A* represents a moiety selected from the group consisting of: ##STR00072## * indicates the position which the double bond of the group of formula (Ia) is bonded to, R.sup.310 and R.sup.320 are each independently hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, or C.sub.5-C.sub.7-cycloalkyl, R.sup.330 is hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, partly fluorinated C.sub.1-C.sub.10-alkyl, perfluorinated C.sub.1-C.sub.10-alkyl, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl or aryloxy-C.sub.1-C.sub.10-alkyl, R.sup.340 is hydrogen, NO.sub.2, CN, COR.sup.350, COOR.sup.350, SO.sub.2R.sup.350 or SO.sub.3R.sup.350, R.sup.350 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, R.sup.410 is hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms and which may be mono- or polysubstituted by hydroxyl, mercapto, halogen, cyano, nitro, —COOM and/or —COOR.sup.420, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl, or an —NHCOR.sup.420 or —N(COR.sup.420).sub.2 radical where the two R.sup.420 in the latter may be the same or different, X is independently CH or N, Y is O, C(CN).sub.2, C(CN)(COOM) or C(CN)(COOR.sup.420), M is alkali metal cation or [NR.sup.420].sub.4.sup.+, and R.sup.420 is hydrogen, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms.

2. The compound of claim 1, wherein R.sup.100 is hydrogen or C.sub.1-C.sub.4-alkyl, and R.sup.200 is aryl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms.

3. The compound of claim 1, wherein when m=1 the donor moiety D is selected from the group consisting of: ##STR00073## R.sup.110, R.sup.120 and R.sup.130 are each independently hydrogen, halogen, hydroxyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-alkylamino, di(C.sub.1-C.sub.10-alkyl)amino, C.sub.1-C.sub.10-alkylamino- or di(C.sub.1-C.sub.10-alkyl)aminosulfonylamino, C.sub.1-C.sub.10-alkylsulfonylamino, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or an —NHCOR.sup.170 or —NHCOOR.sup.170 radical, R.sup.140, R.sup.150 and R.sup.160 are each independently hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or in case R.sup.140 and R.sup.160 or R.sup.150 and R.sup.160 are bonded to adjacent carbon atoms these pairs of groups may—together with the carbon atoms to which they are bonded-form a five- or six-membered ring in which one CH.sub.2 group may be replaced by an oxygen atom, R.sup.170 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms and in case of two moities for m=2 may vary independently of each other, R.sup.210, R.sup.220, R.sup.230 and R.sup.240 are each independently aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.10-cycloalkyl, or R.sup.210 and R.sup.220 and/or R.sup.230 and R.sup.240 form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR.sup.210R.sup.220 and R.sup.110 are bonded to adjacent carbon atoms, R.sup.110 and R.sup.210 or R.sup.110 and R.sup.220—together with the nitrogen atom of the moiety NR.sup.210R.sup.220 and the carbon atom to which the moieties NR.sup.210R.sup.220 and R.sup.110 are bonded—form a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring, R.sup.250 and R.sup.260 are each independently C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl or aryloxy-C.sub.1-C.sub.10-alkyl, Z is O or S, when m=2 the donor moiety D is selected from the group consisting of: ##STR00074## wherein R.sup.170 is defined above and in case of two moities may vary independently of each other, and when m=3 the donor moiety D is selected from the group consisting of: ##STR00075## wherein R.sup.170 is defined above.

4. The compound of claim 1, wherein when m=1 the donor moiety D is selected from the group consisting of: ##STR00076## when for m=2 the donor moiety D is selected from the group consisting of: ##STR00077## and when m=3 the donor moiety D is selected from the group consisting of: ##STR00078##

5. The compound of claim 1, wherein when m=1 the donor moiety D is a represented by formula (D01): ##STR00079## R.sup.110 is hydrogen, halogen, hydroxyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.7-cycloalkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-alkylamino, di(C.sub.1-C.sub.10-alkyl)amino, C.sub.1-C.sub.10-alkylamino- or di(C.sub.1-C.sub.10-alkyl)aminosulfonylamino, C.sub.1-C.sub.10-alkylsulfonylamino, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or an —NHCOR.sup.170 or —NHCOOR.sup.170 radical, R.sup.170 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, R.sup.210 and R.sup.220 are each independently aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, C.sub.5-C.sub.10-cycloalkyl, or R.sup.210 and R.sup.220 form, together with the nitrogen atom to which they are bonded, a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom, or in case NR.sup.210R.sup.220 and R.sup.110 are bonded to adjacent carbon atoms, R.sup.110 and R.sup.210 or R.sup.110 and R.sup.220—together with the nitrogen atom of the moiety NR.sup.210R.sup.220 and the carbon atom to which the moieties NR.sup.210R.sup.220 and R.sup.110 are bonded—form a five- or six-membered ring in which one CH.sub.2 group not adjacent to the nitrogen atom may be replaced by an oxygen atom and which five- or six-membered ring may be fused to another five- or six-membered saturated or unsaturated ring, when m=2 the donor moiety D is selected from the group consisting of: ##STR00080## wherein R.sup.170 is defined above, and when m=3 the donor moiety D is represented by the formula: ##STR00081##

6. The compound of claim 1, wherein the acceptor moiety A is: represented by the formula (A01): ##STR00082## wherein R.sup.340 is hydrogen, NO.sub.2, CN, COR.sup.350, COOR.sup.350, SO.sub.2R.sup.350 or SO.sub.3R.sup.350, R.sup.350 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, R.sup.410 is hydrogen, C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms and which may be mono- or polysubstituted by hydroxyl, mercapto, halogen, cyano, nitro, —COOM and/or —COOR.sup.420, C.sub.5-C.sub.7-cycloalkyl, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl, or an —NHCOR.sup.420 or —N(COR.sup.420).sub.2 radical where the two R.sup.420 in the latter may be the same or different, M is alkali metal cation or [NR.sup.420].sub.4.sup.+, and R.sup.420 is hydrogen, aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms.

7. The compound of claim 1, wherein the acceptor moiety A is represented by the formula (A01): ##STR00083## wherein R.sup.340 is hydrogen, NO.sub.2, CN, COR.sup.350, COOR.sup.350, SO.sub.2R.sup.350 or SO.sub.3R.sup.350, R.sup.350 is aryl, aryl-C.sub.1-C.sub.10-alkyl, aryloxy-C.sub.1-C.sub.10-alkyl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms, R.sup.410 is aryl or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms and which is terminally substituted by hydroxyl, —COOM or —COOR.sup.420, M is alkali metal cation or [NR.sup.420].sub.4.sup.+, and R.sup.420 is hydrogen or C.sub.1-C.sub.10-alkyl which in case of C.sub.2-alkyl may be interrupted by one and in case of C.sub.3-C.sub.10-alkyl by one or two nonadjacent oxygen atoms.

8. The compound of claim 1, wherein m is 1.

9. The compound of claim 1, wherein m is 2.

10. The compound of claim 1, wherein m is 3.

11. A dye-sensitized solar cell comprising the compound of claim 1.

12. A method of producing a dye-sensitized solar cell comprising incorporating the compound of claim 1 into a dye-sensitized solar cell.

Description

EXPERIMENTAL PART

A) Preparation of Compounds According to the Invention

Materials and Methods

(1) Chemicals were purchased from Aldrich and TCI Europe and used as received without further purification. 2-Iodofluorene (S. H. Lee, T. Nakamura, T. Tsutsui, Org. Lett. 2001, 3, 2005), 9,9-dimethyl-2-iodofluorene (C. H. Huang, S. H. Yang, K. B. Chen, C. S. Hsu, J. Polym. Sci. Part A: Polym. Chem. 2006, 44, 519), and N,N-bis(9,9-dimethylfluoren-2-yl)aniline (H. Doi, M. Kinoshita, K. Okumoto, Y. Shirota, Chem. Mater. 2003, 15, 1080) were synthesized according to the citations in parentheses, 4-[bis(4-methylphenyl)-amino]benzaldehyde was purchased from TCI Europe.

(2) The .sup.1H and .sup.13C NMR spectra were taken on Varian Unity Inova (300 MHz) spectrometer at room temperature. All the data are given as chemical shifts in δ (ppm), (CH.sub.3).sub.4Si (TMS, 0 ppm) was used as an internal standard. The course of the reactions products were monitored by TLC on ALUGRAM SIL G/UV254 plates and developed with I.sub.2 or UV light. Silica gel (grade 9385, 230-400 mesh, 60 Å, Aldrich) was used for column chromatography. Elemental analysis was performed with an Exeter Analytical CE-440 Elemental. IR-spectroscopy was performed on a Perkin Elmer Spectrum BX II FT-IR System, using KBr pellets. Mass spectra (MS) were recorded on an Aligent 110 (series MS with VL) apparatus. The UV spectra were recorded on a Perkin Elmer Lambda 35 spectrometer. 10.sup.−4 M solution of investigated dye in CHCl.sub.3 and microcell with an internal width of 1 mm was used.

(3) A1) Preparation of Dyes D1 to D9

(4) Generalized Procedure

(5) Condensation of the aldehyde 1 with phenyl hydrazine yielded hydrazone 2

(6) ##STR00024##

(7) which was used in the arylation reaction with 4-fluorobenzaldehyde to yield compound 3 according to Route A)

(8) ##STR00025##

(9) or alkylation reaction with 1-bromopropane and formylation of the alkylated intermediate 4 by the Vilsmeier-Haack method to yield compound 5 according to route B)

(10) ##STR00026##

(11) Finally, condensation of the aldehydes 3 and 5 with rhodanine-3-acetic acid yielded dyes ID-1276 (D1), ID-1261 (D2), ID-1300 (D3), ID-1332 (D4), ID-1464 (D5) and ID-1509 (D7) and with rhodanine-3-benzoic acid dye ID-1465 (D6), respectively. The variables R in the reaction routes shown before can be taken explicitly from the specific synthetic procedures.

Preparation of Dye D1

4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone

(12) ##STR00027##

(13) A mixture of compound 3 (0.76 g, 1.54 mmol; both radicals R equal 4-methylphenyl), rhodanine-3-acetic acid (0.35 g, 1.85 mmol) and ammonium acetate (0.03 g, 0.46 mmol) was refluxed in acetic acid (5.0 mL) for 3 h. Afterwards, water (15 mL) was added and the extraction was done with chloroform. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 7:18 v/v acetone/hexane followed by 7:1:17 v/v acetone/methanol/toluene as an eluent to collect dye D1 as a dark red solid (0.46 g, 45%).

(14) .sup.1H NMR (300 MHz, DMSO-d.sub.6, δ): 7.94-6.69 (m, 24H), 4.58 (s, 2H, CH.sub.2), 2.26 (s, 6H, CH.sub.3);

(15) .sup.13C NMR (75 MHz, DMSO-d.sub.6, δ): 193.48, 168.34, 167.39, 150.98, 149.43, 146.87, 144.85, 143.57, 138.39, 135.38, 133.69, 131.15, 130.85, 128.27, 126.27, 126.89, 125.59, 121.12, 119.08, 117.87, 115.36, 47.02, 30.32, 21.15;

(16) IR (KBr): v=3486 (OH); 3025 (aromatic CH); 2977, 2918, 2859 (aliphatic CH); 1708 (C═O); 1575, 1504 (C═C); 1294 (C═S); 1198, 1175, 1105 (C—N); 863, 815 (CH═CH of 1,4-disubstituted benzenes), 781, 745, 718 (CH═CH of monosubstituted benzene);

(17) Anal. calcd for C.sub.36H.sub.32N.sub.4O.sub.3S.sub.2(%): C, 70.04; H, 4.82; N, 8.38. found: C, 70.19; H, 4.88; N, 8.17.

Preparation of Dye D2

a) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-phenyl-N-propylhydrazone (D2-1; corresponds to compound 4 where both radicals R equal 4-methylphenyl)

(18) ##STR00028##

(19) To a refluxing mixture of compound 2 (1.45 g, 3.70 mmol; both radicals R equal 4-methylphenyl), dissolved in mixture of anhydrous tetrahydrofuran (3 mL) and 1-bromopropane (1 mL), powdered KOH (0.62 g, 11.11 mmol) and anhydrous Na.sub.2SO.sub.4 (0.21 g, 1.48 mmol) were added in three equal portions every 1 h. After 3.5 hours the reaction mixture was extracted with ethyl acetate and distilled water until neutral. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered off and ethyl acetate was removed. The residue was washed with a mixture of 2-propanol and n-hexane (1:1) to give compound D2-1 as yellow solid (1.53 g, 96%).

(20) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.52 (d, J=8.6 Hz, 2H), 7.36 (s, 1H), 7.36-7.20 (m, 4H), 7.09-6.95 (m, 10H), 6.91-6.83 (m, 1H), 3.83 (t, J=7.7 Hz, 2H), 2.30 (s, 6H), 1.78-1.62 (m, 2H), 1.02 (t, J=7.3 Hz, 3H);

(21) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 147.83, 147.28, 145.09, 132.55, 131.07, 130.22, 129.84, 128.99, 126.71, 124.62, 122.45, 119.82, 114.41, 46.77, 20.80, 18.28, 11.35;

(22) Anal. calcd for C.sub.30H.sub.31N.sub.3(%): C, 83.10; H, 7.21; N, 9.69. found: C, 83.33; H, 7.10; N, 9.57.

b) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-(4-formyl)phenyl-N-propylhydrazone (D2-2)

(23) ##STR00029##

(24) Phosphorus oxychloride (0.16 mL, 1.73 mmol) was added dropwise to DMF (0.85 mL, 11.04 mmol), not allowing the temperature of the mixture to rise above 5° C. A solution of 17 (0.50 g, 1.15 mmol) in DMF (2.15 mL) was added, and the resulting mixture was heated at 60° C. for 30 min. The hot reaction mixture was poured into the ice-water, neutralized by adding sodium acetate (0.42 g, 5.19 mmol) aqueous solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 1.5:2:20 v/v acetone/diethyl ether/hexane as an eluent to collect compound D2-2 as a yellow solid (0.18 g, 34%).

(25) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.82 (s, 1H, CHO), 7.79 (d, J=9.0 Hz, 2H), 7.62 (s, 1H), 7.55 (d, J=8.8 Hz, 2H), 7.41 (d, J=8.8 Hz, 2H), 7.12-6.96 (m, 10H), 3.90 (t, J=7.8 Hz, 2H, CH.sub.2CH.sub.2CH.sub.3), 2.32 (s, 6H, CH.sub.3), 1.81-1.66 (m, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.05 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.2CH.sub.3);

(26) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.65, 151.55, 148.89, 144.77, 134.97, 133.15, 131.62, 129.95, 128.55, 128.18, 127.37, 125.01, 121.67, 113.27, 45.94, 20.83, 18.48, 11.27;

(27) Anal. calcd for C.sub.31H.sub.3N.sub.3O (%): C, 80.66; H, 6.77; N, 9.10. found: C, 80.53; H, 6.90; N, 9.02.

c) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-propylhydrazone (D2)

(28) ##STR00030##

(29) A mixture of D2-2 (0.165 g, 0.35 mmol), rhodanine-3-acetic acid (0.08 g, 0.11 mmol), and ammonium acetate (0.01 g, 0.11 mmol) was refluxed in acetic acid (0.6 mL) for 30 min. Afterwards, water (10 mL) was added and the extraction was done with ethyl acetate. The combined organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 23:2 v/v toluene/methanol as an eluent to collect dye D2 as a dark red solid (0.18 g, 80%).

(30) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.62-6.59 (m, 19H), 4.70 (s, 2H, CH.sub.2), 3.62 (t, J=7.8 Hz, 2H, CH.sub.2CH.sub.2CH.sub.3), 2.30 (s, 6H, CH.sub.3), 1.69-1.40 (m, 2H, CH.sub.2CH.sub.2CH.sub.3), 0.90 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.2CH.sub.3);

(31) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 192.6, 170.0, 167.3, 148.46, 144.83, 143.59, 135.1, 134.12, 132.91, 129.91, 128.99, 128.18, 127.13, 125.94, 124.87, 121.74, 113.82, 47.1, 45.69, 21.2, 20.8, 18.10, 11.23;

(32) IR (KBr): v=3391 (OH), 3025 (aromatic CH); 2961, 2919, 2871 (aliphatic CH); 1705 (C═O); 1601, 1575, 1504 (C═C); 1293 (C═S); 1181, 1100 (C—N); 815 (CH═CH of 1,4-disubstituted benzenes);

(33) Anal. calcd for C.sub.36H.sub.34N.sub.4O.sub.3S.sub.2(%): C, 68.11; H, 5.40; N, 8.83. found: C, 68.00; H, 5.26; N, 8.61.

Preparation of Dye D3

a) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde (D3-1; corresponds to compound 1 where both radicals R equal 9,9-dimethyl-9H-fluoren-2-yl)

(34) ##STR00031##

(35) Phosphorus oxychloride (1.30 mL, 14.13 mmol) was added portion-wise to DMF (1.1 mL, 14.13 mmol), not allowing the temperature of the mixture to rise above 5° C. N,N-bis(9,9-dimethylfluoren-2-yl)aniline (4.50 g, 9.42 mmol) was then added and the resulting mixture was heated at 90° C. for 4 h. The hot reaction mixture was poured into ice-water and neutralized by adding sodium acetate (3.47 g, 42.39 mmol) aqueous solution. After extraction with ethyl acetate and distilled water, the organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent was evaporated. The crude product was purified by column chromatography using 3:22 v/v acetone/n-hexane as an eluent to collect compound D3-1 as a yellow solid (4.20 g, 88%).

(36) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.83 (s, 1H, CHO), 7.76-7.60 (m, 6H), 7.43-7.11 (m, 12H), 1.42 (s, 12H, CH.sub.3);

(37) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.36, 155.37, 153.59, 145.58, 138.47, 136.11, 131.29, 129.21, 127.03, 124.78, 122.55, 120.90, 120.27, 119.96, 119.72, 46.90, 26.96;

(38) Anal. calcd for C.sub.37H.sub.31NO (%): C, 87.89; H, 6.18; N, 2.77. found: C, 87.95; H, 6.27; N, 2.70.

b) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde-N-phenylhydrazone (D3-2; corresponds to compound 2 where both R equal 9,9-dimethyl-9H-fluoren-2-yl)

(39) ##STR00032##

(40) To compound D3-1 (3.50 g, 6.91 mmol) dissolved in a mixture of toluene (10 mL) and 2-propanol (2 mL), phenylhydrazine (1.00 mL, 10.16 mmol) was added. The mixture was refluxed until the arylaldehyde D3-1 disappeared (TLC, v/v acetone/n-hexane, 1:4). After reaction was complete solvents were removed under reduced pressure. Yellow crystals of 20 (3.58 g, 87%), formed upon adding the mixture of 2-propanol (15 mL) and toluene (4 mL), were filtered off and washed with 2-propanol. The crude product was used in the next step without additional purification.

c) 4-[Bis(9,9-dimethy-9H-fluoren-2-yl)amino]benzaldehyde-N-(4-formylphenyl)-N-phenylhydrazone (D3-3; corresponds to compound 3 where both R equal 9,9-dimethyl-9H-fluoren-2-yl)

(41) ##STR00033##

(42) A mixture of compound D3-2 (3.19 g, 5.36 mmol), 4-fluorobenzaldehyde (1.73 mL, 16.10 mmol) and K.sub.2CO.sub.3 (4.45 g, 32.20 mmol) was refluxed in 25 mL anhydrous DMF under argon atmosphere for 16 h. After cooling to room temperature, 30 mL of distilled water were added and extraction was done with ethyl acetate. The organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 10:1:14 v/v toluene/ethyl acetate/n-hexane as an eluent to collect compound D3-3 as a yellow solid (2.10 g, 56%).

(43) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.81 (s, 1H, CHO), 7.73 (d, J=9.0 Hz, 2H), 7.68-7.49 (m, 8H), 7.41-7.13 (m, 18H), 7.11 (d, J=2.0 Hz, 1H), 7.08 (d, J=2.0 Hz, 1H), 1.40 (s, 12H, CH.sub.3);

(44) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.68, 155.08, 153.47, 151.99, 148.83, 146.76, 138.86, 138.78, 138.36, 134.61, 131.36, 131.09, 129.85, 129.41, 128.85, 128.69, 127.72, 126.99, 126.60, 123.50, 123.03, 122.47, 120.63, 119.45, 118.96, 114.04, 46.81, 27.00;

(45) IR (KBr): v=3035 (aromatic CH); 2956, 2921, 2858, 2725 (aliphatic CH); 1689 (CHO); 1598, 1588, 1564, 1505, 1487 (C═C); 1157, 1117 (C—N); 867, 826 (CH═CH of 1,4-disubstituted benzene); 778, 758, 736 (CH═CH of monosubstituted benzene).

(46) Anal. calcd for C.sub.50H.sub.41N.sub.3O (%): C, 85.81; H, 5.90; N, 6.00. found: C, 85.70; H, 5.94; N, 6.03.

d) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone (D3)

(47) ##STR00034##

(48) A mixture of compound D3-3 (0.70 g, 1.00 mmol), rhodanine-3-acetic acid (0.23 g, 1.2 mmol), and ammonium acetate (0.02 g, 0.29 mmol) was refluxed in acetic acid (7 mL) for 3.5 h. Afterwards, 20 mL of water was added and the extraction was done with ethyl acetate. The organic layer was washed with distilled water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using toluene followed by 23:2 v/v toluene/methanol as an eluent to collect dye D3 as a dark red solid (0.58 g, 67%).

(49) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.96-6.85 (m, 30H), 4.90 (s, 2H, CH.sub.2), 1.46 (s, 12H, CH.sub.3);

(50) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 192.61, 171.46, 167.44, 155.34, 155.08, 153.59, 153.47, 146.70, 145.56, 138.79, 138.51, 134.55, 132.66, 131.04, 129.71, 129.34, 128.99, 128.18, 127.71, 126.99, 126.60, 125.27, 124.58, 123.50, 123.02, 122.47, 120.89, 120.64, 120.04, 119.71, 119.45, 118.96, 114.96, 46.88, 46.80, 26.99;

(51) IR (KBr): v=3545 (OH); 3034 (aromatic CH); 2956, 2920, 2858 (aliphatic CH); 1710

(52) (C═O); 1574, 1504, 1488 (C═C); 1297 (C═S); 1198, 1175, 1135, 1104 (C—N); 868, 824 (CH═CH of 1,4-disubstituted benzene); 777, 757, 735 (CH═CH of monosubstituted benzene);

(53) Anal. calcd. for C.sub.55H.sub.44N.sub.4O.sub.3S.sub.2(%): C, 75.66; H, 5.08; N, 6.42. found: C, 75.74; H, 5.16; N, 6.32.

Preparation of Dye D4

a) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde-N-phenyl-N-propylhydrazone (D4-1; corresponds to compound 4 where both radicals R equal 9,9-dimethyl-9H-fluoren-2-yl)

(54) ##STR00035##

(55) To a refluxing mixture of compound 2 (3.05 g, 5.11 mmol; both radicals R equal 9,9-dimethyl-9H-fluoren-2-yl), 1-bromopropane (2.77 mL, 30.66 mmol) in anhydrous THF (5 mL), powdered KOH (1.06 g, 18.89 mmol) and anhydrous Na.sub.2SO.sub.4 (0.40 g, 2.81 mmol) were added in three equal portions every 1 h. After 3.5 hours the reaction mixture was extracted with ethyl acetate and distilled water until neutral. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered off and ethyl acetate was removed. The crude product was purified by column chromatography using 3:22 v/v acetone/n-hexane as an eluent to collect compound D4-1 as a yellow solid (3.01 g, 92%).

(56) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.68-7.55 (m, 6H), 7.51 (s, 1H), 7.42-7.05 (m, 16H), 6.89 (t, J=6.9 Hz, 1H), 3.86 (t, J=7.7 Hz, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.79-1.65 (m, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.41 (s, 12H, CH.sub.3), 1.03 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.2CH.sub.3);

(57) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 155.02, 153.49, 147.51, 147.15, 138.93, 134.16, 131.20, 130.86, 129.03, 126.96, 126.86, 126.45, 123.84, 123.17, 122.45, 120.57, 120.02, 119.38, 118.59, 114.54, 46.88, 46.81, 27.02, 18.31, 11.37;

(58) Anal. calcd for C.sub.46H.sub.43N.sub.3(%): C, 86.62; H, 6.79; N, 6.59. found: C, 86.70; H, 6.69; N, 6.61.

b) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde-N-4-formylphenyl-N-propylhydrazone (D4-2)

(59) ##STR00036##

(60) Phosphorus oxychloride (1.06 mL, 11.60 mmol) was added drop wise to DMF (5.70 mL, 74.07 mmol) not allowing the temperature of the mixture to rise above 5° C. A solution of 22 (5.00 g, 7.84 mmol) in DMF (14.5 mL) was then added and the resulting mixture was heated at 60° C. for 50 min. The hot reaction mixture was poured into ice-water, neutralized by adding sodium acetate (2.85 g, 34.80 mmol) aqueous solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent was evaporated. Crude product was purified by column chromatography using 3:22 v/v acetone/hexane as an eluent to collect compound D4-2 as a yellow solid (1.16 g, 22%).

(61) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.87 (s, 1H, CHO), 7.85 (d, J=8.9 Hz, 2H), 7.74-7.63 (m, 7H), 7.52-7.22 (m, 12H), 7.18 (d, J=2.0 Hz, 1H), 7.15 (d, J=2.0 Hz, 1H), 3.96 (t, J=7.8 Hz, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.87-1.72 (m, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.47 (s, 12H, CH.sub.3), 1.12 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.2CH.sub.3);

(62) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.61, 155.13, 153.52, 151.57, 148.64, 146.86, 138.83, 134.78, 134.60, 131.62, 129.56, 128.39, 127.55, 127.00, 126.60, 123.51, 123.22, 122.49, 120.64, 119.46, 118.96, 113.41, 46.84, 46.08, 27.02, 18.51, 11.28; IR (KBr): v=3747, 3186, 3035, 3010 (aromatic CH); 2957, 2921, 2858, 2724 (aliphatic CH); 1676 (CHO); 1595, 1565, 1505, 1486 (C═C); 1163, 1109 (C—N); 826 (CH═CH of 1,4-disubstituted benzene);

(63) Anal. calcd. for C.sub.47H.sub.43N.sub.3O (%): C, 84.78; H, 6.51; N, 6.31. found: C, 84.82; H, 6.59; N, 6.41.

c) 4-[Bis(9,9-dimethyl-9H-fluoren-2-yl)amino]benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-propylhydrazone (D4)

(64) ##STR00037##

(65) A mixture of 23 (0.58 g, 0.88 mmol) and rhodanine-3-acetic acid (0.20 g, 1.05 mmol) was refluxed in acetic acid (3.0 mL) for 2 h. Afterwards, water (15 mL) was added and the extraction was done with ethyl acetate. The organic layer was washed with distilled water, dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using toluene followed by 23:2 v/v toluene/methanol as an eluent to collect dye D4 as a dark red solid (0.43 g, 58%).

(66) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.74-7.52 (m, 6H), 7.47-7.03 (m, 19H), 4.87 (s, 2H, CH.sub.2), 3.87 (t, J=7.8 Hz, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.78-1.65 (m, 2H, CH.sub.2CH.sub.2CH.sub.3), 1.41 (s, 12H, CH.sub.3), 1.04 (t, J=7.3 Hz, 3H, CH.sub.2CH.sub.2CH.sub.3);

(67) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 192.58, 171.04, 167.31, 155.36, 155.08, 153.58, 146.82, 145.51, 138.81, 138.47, 136.02, 134.56, 132.89, 132.51, 128.98, 128.17, 126.99, 125.24, 124.60, 123.48, 122.53, 120.89, 120.64, 120.07, 119.71, 119.44, 118.93, 114.18, 46.89, 46.80, 44.65, 27.00, 18.49, 11.29;

(68) IR (KBr): v=3635 (OH); 3032 (aromatic CH); 2957, 2921, 2859 (aliphatic CH); 1709 (C═O); 1602, 1573, 1505, 1486 (C═C); 1298 (C═S); 1182, 1100 (C—N); 823 (CH═CH of 1,4-disubstituted benzene);

(69) Anal. calcd. for C.sub.52H.sub.46N.sub.4O.sub.3S.sub.2(%): C, 74.43; H, 5.53; N, 6.68. found: C, 74.55; H, 5.61; N, 6.59.

Preparation of Dye D5

a) 4-(diphenylamino)benzaldehyde-N-phenylhydrazone (D5-1; corresponds to compound 2 where both radicals R equal phenyl)

(70) ##STR00038##

(71) Compound D5-1 was prepared according to Urnikaite S., Daskeviciene M., Malinauskas T., Jankauskas V., Getautis V., Monast. Chem., 2009, 140(12), 2005-2007.

b) 4-(diphenylamino)benzaldehyde-N-(4-formyl)phenyl-N-phenylhydrazone (D5-2; corresponds to compound 3 where both radicals R equal phenyl)

(72) ##STR00039##

(73) A mixture of 1 (3.00 g, 8.25 mmol), 4-fluorobenzaldehyde (2.66 ml, 24.76 mmol) and K.sub.2CO.sub.3 (6.80 g, 49.52 mmol) was refluxed in 25 mL anhydrous DMF under argon atmosphere for 15 h. After cooling to room temperature, 30 mL of distilled water were added and extraction was done with ethyl acetate. The organic layer was washed with distilled water, dried over anhydrous sodium sulfate and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 10:1:14 v/v toluene/ethyl acetate/hexane as an eluent to collect compound D5-2 as a yellow solid (1.98 g, 52%).

(74) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.80 (s, 1H), 7.72 (d, J=8.9 Hz, 2H), 7.68-7.58 (m, 2H), 7.57-7.43 (m, 3H), 7.30-6.97 (m, 17H);

(75) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.68, 151.97, 148.65, 147.16, 138.80, 138.29, 131.33, 131.06, 129.81, 129.30, 128.97, 128.74, 128.61, 127.65, 124.76, 123.38, 122.69, 113.98;

(76) IR (KBr): v (cm.sup.−1)=3058, 3033 (aromatic CH); 2802, 2727, 2623 (aliphatic CH); 1688 (CHO); 1588, 1563, 1505, 1487 (C═C); 1157, 1117 (C—N); 863, 826 (CH═CH of 1,4-disubstituted benzenes), 753, 738 (CH═CH of monosubstituted benzenes);

(77) Anal. calcd. for C.sub.32H.sub.25N.sub.3O (%): C, 82.20; H, 5.39; N, 8.99. found: C, 82.11; H, 5.41; N, 9.03.

c) 4-(diphenylamino)benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone (D5)

(78) ##STR00040##

(79) A mixture of compound D5-2 (0.31 g, 0.67 mmol), rhodanine-3-acetic acid (0.15 g, 0.80 mmol) and ammonium acetate (0.015 g, 0.20 mmol) was refluxed in acetic acid (4.0 mL) for 4.5 h. Afterwards, 10 mL of water were added and the extraction was done with chloroform. The organic layer was washed with distilled water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 10:1:14 v/v toluene/ethyl acetate/hexane followed by 23:2 v/v toluene/methanol as an eluent to collect dye D5 as a dark red solid (0.28 g, 67%).

(80) .sup.1H NMR (300 MHz, 50% DMSO-d.sub.6/CDCl.sub.3, δ): 7.82-6.64 (m, 25H), 4.63 (s, 2H);

(81) .sup.13C NMR (75 MHz, 50% DMSO-d.sub.6/CDCl.sub.3, δ): 191.02, 165.29, 147.28, 146.59, 145.22, 144.14, 136.20, 131.63, 131.05, 130.68, 129.48, 128.04, 127.72, 127.22, 126.96, 126.46, 126.03, 124.26, 122.95, 121.82, 120.65, 113.15, 44.93;

(82) IR (KBr): v (cm.sup.−1)=3614 (OH); 3032 (aromatic CH), 2924 (aliphatic CH); 1709 (C═O); 1575, 1504 (C═C); 1294 (C═S); 1198, 1175, 1135, 1104 (C—N); 823 (CH═CH of 1,4-disubstituted benzenes); 752, 723 (CH═CH of monosubstituted benzenes);

(83) Anal. calcd. for C.sub.37H.sub.28N.sub.4O.sub.3S.sub.2(%): C, 69.35; H, 4.40; N, 8.74. found: C, 69.28; H, 4.42; N, 8.77.

Preparation of Dye D6

a) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-phenylhydrazone (D6-1; corresponds to compound 2 where both radicals R equal 4-methylphenyl)

(84) ##STR00041##

(85) To compound 1 (3.50 g, 6.91 mmol; both radicals R equal 4-methylphenyl) dissolved in toluene (10 mL) and 2-propanol (2 mL), phenylhydrazine (1.00 mL, 10.16 mmol) was added. The mixture was refluxed until the compound 1 disappeared (TLC, acetone: n-hexane=1:4). At the end of the reaction, the mixture was cooled to room temperature. Yellow crystals, having formed upon standing, were filtered off and washed with a mixture of 2-propanol and n-hexane (1:1) to give the corresponding compound D6-2 (4.03, 89%), which was used in the next reaction without further purification.

b) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-(4-formylphenyl)-N-phenylhydrazone (D6-3; corresponds to compound 3 where both radicals R equal 4-methylphenyl)

(86) ##STR00042##

(87) A mixture of D6-2 (3.27 g, 8.35 mmol), 4-fluorobenzaldehyde (2.69 ml, 25.07 mmol), and K.sub.2CO.sub.3 (6.93 g, 50.14 mmol) were refluxed in anhydrous DMF (25 mL) under argon atmosphere for 24 h. After cooling to room temperature, distilled water (30 mL) was added and mixture was extracted with ethyl acetate, dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent was evaporated. The crude product was purified by column chromatography using 10:1:14 v/v toluene/ethyl acetate/n-hexane as an eluent to collect compound D6-3 as a yellow solid (2.76 g, 67%).

(88) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.80 (s, 1H, CHO), 7.72 (d, J=8.9 Hz, 2H), 7.67-7.49 (m, 2H), 7.44 (d, J=8.8 Hz, 2H), 7.27-6.93 (m, 16H), 2.31 (s, 6H, CH.sub.3);

(89) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.70, 152.04, 149.09, 144.65, 139.11, 138.35, 133.14, 131.97, 131.35, 131.04, 129.93, 129.84, 129.33, 127.57, 125.02, 121.42, 115.03, 113.93, 20.81;

(90) IR (KBr): v=3347, 3071, 3054 (aromatic CH); 2951, 2850, 2817, 2764 (aliphatic CH); 1685 (CHO); 1603, 1678, 1505, 1465 (C═C); 1169, 1157, 1112 (C—N); 875, 822 (CH═CH of 1,4-disubstituted benzenes), 796, 735 (CH═CH of monosubstituted benzene);

(91) Anal. calcd for C.sub.34H.sub.29N.sub.3O (%): C, 82.40; H, 5.90; N, 8.48. found: C, 82.31; H, 5.95; N, 8.53.

c) 4-(4,4′-dimethyldiphenylamino)benzaldehyde-N-4-[3-(4-carboxy)phenyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl]phenyl-N-phenylhydrazone (D6)

(92) ##STR00043##

(93) A mixture of D6-3 (0.30 g, 0.61 mmol), 4-(4-oxo-2-thioxo-1,3-thiazolidin-3-yl)benzoic acid (0.18 g, 0.73 mmol) and ammonium acetate (0.017 g, 0.22 mmol) was refluxed in acetic acid (3.0 mL) for 6 h. At the end of the reaction, the mixture was cooled to room temperature. The crystals formed upon standing were filtered off and washed with 2-propanol. The crude product was purified by column chromatography using 2:23 v/v methanol/toluene as an eluent to collect dye D6 as a dark red solid (0.196 g, 72%).

(94) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 8.25 (d, J=8.4 Hz, 2H), 7.76-6.91 (m, 25H), 2.34 and 2.31 (two s of isomeric CH.sub.3, 6H);

(95) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 192.86, 170.61, 167.49, 149.54, 149.17, 144.67, 139.81, 139.20, 138.25, 134.78, 133.20, 132.68, 131.32, 131.07, 130.34, 129.96, 129.36, 128.83, 127.63, 126.20, 125.07, 121.43, 119.15, 117.45, 114.87, 20.94, 20.83;

(96) IR (KBr): v=3431 (OH); 3025 (aromatic CH); 2918, 2857 (aliphatic CH); 1698 (C═O); 1661, 1574, 1504, (C═C); 1294 (C═S); 1173, 1150 (C—N); 858, 815, 796 (CH═CH of 1,4-disubstituted benzenes); 754, 728, 716, 697 (CH═CH of monosubstituted benzene);

(97) Anal. calcd for C.sub.44H.sub.34N.sub.4O.sub.3S.sub.2(%): C, 72.31; H, 4.69; N, 7.67. found: C, 72.36; H, 4.70; N, 7.63.

Preparation of Dye D7

a) 4-(4-methyldiphenylamino)benzaldehyde-N-phenylhydrazone (D7-1; corresponds to compound 2 where one radical R equals phenyl and the other radical R 4-methylphenyl)

(98) ##STR00044##

(99) To 4-[(4-methyldiphenyl)amino]benzaldehyde (6 g, 20.88 mmol) dissolved in toluene (30 mL) and 2-propanol (5 mL), phenylhydrazine (3.00 mL, 31.32 mmol) was added. The mixture was refluxed until the arylaldehyde disappeared (TLC, acetone:n-hexane=3:22). At the end of the reaction, the mixture was cooled to room temperature. Yellow crystals, having formed upon standing, were filtered off and washed with a mixture of 2-propanol and n-hexane (1:1) to give the corresponding phenylhydrazone D7-1 (6.26, 80%), which was used in the next reaction without further purification.

b) 4-(4-methyldiphenylamino)benzaldehyde-N-(4-formyl)phenyl-N-phenylhydrazone (D7-2)

(100) ##STR00045##

(101) A mixture of compound D7-1 (2.65 g, 7.02 mmol), 4-fluorobenzaldehyde (1.63 mL, 15.19 mmol) and K.sub.2CO.sub.3 (4.0 g, 28.94 mmol) was refluxed in 20 mL anhydrous DMF under argon atmosphere for 12 h. After cooling to room temperature, 40 mL of distilled water were added and extraction was done with ethyl acetate. The organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 1:24 v/v acetone/n-hexane as an eluent to collect compound D7-2 as a yellow solid (2.35 g, 70%).

(102) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.80 (s, 1H, CHO), 7.72 (d, J=8.9 Hz, 2H), 7.68-7.49 (m, 3H), 7.46 (d, J=8.7 Hz, 2H), 7.29-6.93 (m, 16H), 2.31 (s, 3H);

(103) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.65, 152.02, 148.87, 147.29, 144.56, 138.97, 138.37, 133.46, 131.33, 131.05, 130.01, 129.83, 129.35, 129.22, 128.60, 128.30, 127.62, 125.37, 124.39, 123.06, 122.10, 113.09, 20.84;

(104) IR (KBr): v=3034 (aromatic CH); 2921, 2804, 2728, 2627 (aliphatic CH); 1688 (C═O); 1599, 1588, 1562, 1505, 1489 (C═C); 1157, 1116, 1097 (C—N); 824, 797 (CH═CH of 1,4-disubstituted benzenes); 754, 735, 725, 698 (CH═CH of monosubstituted benzenes);

(105) Anal. calcd for C.sub.33H.sub.27N.sub.3O (%): C, 82.30; H, 5.65; N, 8.73. found: C, 82.33; H, 5.71; N, 8.83.

c) 4-(4-methyldiphenylamino)benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone (D7)

(106) ##STR00046##

(107) A mixture of D7-2 (1.20 g, 2.49 mmol), rhodanine-3-acetic acid (0.57 g, 2.99 mmol), and ammonium acetate (0.06 g, 0.75 mmol) was refluxed in acetic acid (15 mL) for 3.5 h. Afterwards, water (40 mL) was added and the extraction was done with ethyl acetate. The organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 23:2 v/v toluene/methanol as an eluent to collect dye D7 as a dark red solid (0.45 g, 28%).

(108) .sup.1H NMR (300 MHz, 50% DMSO-d.sub.6/CDCl.sub.3, δ): 7.84-6.74 (m, 24H), 4.62 (s, 2H), 2.32 and 2.29 (two s of isomeric CH.sub.3, 3H);

(109) IR (KBr): v=3481 (OH); 3026 (aromatic CH); 2920, 2853, 2604 (aliphatic CH); 1706 (C═O); 1591, 1577, 1504, 1491 (C═C); 1293 (C═S); 1175, 1136, 1105 (C—N); 863, 824, 779 (CH═CH of 1,4-disubstituted benzenes); 750, 696 (CH═CH of monosubstituted benzenes);

(110) Anal. calcd for C.sub.38H.sub.30N.sub.4O.sub.3S.sub.2(%): C, 69.70; H, 4.62; N, 8.56. found: C, 69.68; H, 4.60; N, 8.66.

A2) Preparation of Dyes D8 and D9

(111) Similar to the preparation of dyes D1 to D7, condensation of dialdehydes with the corresponding hydrazine derivatives yielded dihydrazones, which were used in arylation (with 4-fluorobenzaldehyde) or alkylation (with 1-bromononane) reactions and the resulting alkylated intermediate was subjected to a Vilsmeier-Haack reaction and the mono-formylated dihydrazone was isolated. Finally, condensation of the obtained aldehydes with rhodanine-3-acetic acid yielded dyes ID-1370 (D8) and ID-1492 (D9).

(112) The detailed synthetic procedures are as follows:

Preparation of Dye D8

a) 4-(4-formyl-4′-methyldiphenylamino)benzaldehyde (D8-1)

(113) ##STR00047##

(114) Compound D8-1 was prepared according to Getautis V., Daskeviciene M., Malinauskas T., Stanisauskaite A., Stumbraite J., Molecules 2006, 11, 64-71.

b) 4-(4-formyl-4′-methyldiphenylamino)benzaldehyde bis(N-phenylhydrazone) (D8-2)

(115) ##STR00048##

(116) To compound D8-1 (2.76 g, 8.75 mmol), dissolved in tetrahydrofuran (8 mL) and 2-propanol (22 mL), phenylhydrazine (2.15 mL, 21.88 mmol) was added. The mixture was refluxed until the aldehyde disappeared. After completion of the reaction, the mixture was cooled to room temperature and crystals having formed upon standing were filtered off and washed with 2-propanol to give compound D8-2 (4.03 g, 93%), which was used in the next step without further purification.

b) 4-(4-formyl-4′-methyldiphenylamino)benzaldehyde bis[N-(4-formyl)phenyl-N-phenylhydrazone] (D8-3)

(117) ##STR00049##

(118) A mixture of D8-2 (2.80 g, 5.65 mmol), 4-fluorobenzaldehyde (1.82 mL, 16.95 mmol) and K.sub.2CO.sub.3 (4.68 g, 33.89 mmol) was refluxed in 21 mL anhydrous DMF under argon atmosphere for 20 h. After cooling to room temperature, 30 mL of distilled water were added and extraction was done with ethyl acetate. The organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. After evaporation of the solvent, the crude product was purified by column chromatography using 3:3:19 v/v acetone/diethyl ether/n-hexane as an eluent to collect 13 as a yellow solid (1.39 g, 35%).

(119) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.80 (s, 2H), 7.78-7.38 (m, 14H), 7.30-6.93 (m, 18H);

(120) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 151.94, 148.13, 144.06, 138.63, 138.27, 134.06, 131.33, 131.08, 130.14, 129.79, 129.41, 129.22, 128.68, 127.68, 125.66, 123.10, 114.03, 20.87;

(121) Anal. calcd for C.sub.47H.sub.37N.sub.5O.sub.2(%): C, 80.21; H, 5.30; N, 9.95. found: C, 80.19; H, 5.43; N, 9.92.

c) 4-(4-formyl-4′-methyldiphenylamino)benzaldehyde bis[N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone] (D8)

(122) ##STR00050##

(123) A mixture of D8-3 (0.95 g, 1.35 mmol), rhodanine-3-acetic acid (0.62 g, 2.19 mmol) and ammonium acetate (0.06 g, 0.81 mmol) was refluxed in acetic acid (20 mL) for 22 h. Afterwards, water (30 mL) was added and the extraction was done with toluene. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 7:18 v/v acetone/n-hexane followed by 3:22 v/v toluene/methanol as an eluent to collect dye D8 as a dark red solid (0.26 g, 19%).

(124) .sup.1H NMR (300 MHz, 50% DMSO-d.sub.6/CDCl.sub.3): •=8.13-6.72 (m, 34H), 4.70 (s, 4H), 2.31 (s, 3H);

(125) Anal. calcd for C.sub.57H.sub.43N.sub.7O.sub.6S.sub.4(%): C, 65.19; H, 4.13; N, 9.34. found: C, 65.11; H, 4.15; N, 9.33.

Preparation of Dye D9

a) 4-(4-formyldiphenylamino)benzaldehyde bis(N-phenylhydrazone) (D9-1)

(126) ##STR00051##

(127) To D8-1 (11.55 g, 38.32 mmol), dissolved in toluene (50 mL), phenylhydrazine (9.0 mL, 91.97 mmol) was added. The mixture was refluxed until the aldehyde disappeared (TLC, acetone:n-hexane=7:18). At the end of the reaction, the mixture was cooled to room temperature. The crystals having formed upon standing were filtered off and washed with 2-propanol to give compound D9-1 (15.0 g, 82%), which was used in the next reaction without further purification.

b) 4-(4-formyldiphenylamino)benzaldehyde bis(N-nonyl-N-phenylhydrazone) (D9-2)

(128) ##STR00052##

(129) To a refluxing mixture of compound D9-1 (5.0 g, 10.38 mmol), 1-bromononane (15.0 mL, 78.78 mmol) in anhydrous THF (30 mL), powdered KOH (1.92 g, 34.22 mmol) and anhydrous Na.sub.2SO.sub.4 (0.60 g, 4.22 mmol) were added in three equal portions every 1 h. After 19 hours the reaction mixture was extracted with ethyl acetate and distilled water until neutral. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered off and ethyl acetate was removed. The crude product was purified by column chromatography using n-hexane to collect unreacted 1-bromononane, followed by 3:22 v/v toluene/n-hexane as an eluent to collect compound D9-2 as a yellow solid (6.72 g, 88%).

(130) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.58 (d, J=8.7 Hz, 4H), 7.48 (s, 2H, N═CH), 7.39-7.19 (m, 10H), 7.18-7.07 (m, 6H), 7.07-7.00 (m, 1H), 6.93-6.84 (m, 2H), 3.88 (t, J=7.5 Hz, 4H), 1.75-1.59 (m, 4H), 1.49-1.18 (m, 24H), 0.88 (t, J=6.5 Hz, 6H, CH.sub.2CH.sub.3);

(131) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 147.31, 147.18, 147.06, 131.48, 130.68, 129.28, 129.03, 126.86, 124.56, 123.96, 123.14, 119.98, 114.50, 45.23, 31.83, 29.53, 29.41, 29.23, 27.08, 24.81, 22.64, 14.09;

(132) elemental analysis calcd (%) for C.sub.50H.sub.63N.sub.5: C, 81.81; H, 8.65; N, 9.54. found: C, 81.89; H, 8.72; N, 9.55.

c) 4-[(N-nonyl-N-phenylhydrazin-2-ylmethyl)diphenylamino]benzaldehyde-N-(4-formyl)phenyl-N-nonylhydrazone (D9-3)

(133) ##STR00053##

(134) Phosphorus oxychloride (0.47 mL, 5.07 mmol) was added dropwise to DMF (2.85 mL, 37.03 mmol), not allowing the temperature of the mixture to rise above 5° C. A solution of D9-2 (2.48 g, 3.38 mmol) in DMF (6.0 mL) was added and the resulting mixture was heated at 60° C. for 2 h. The hot reaction mixture was poured into the ice water, neutralized by addition of sodium acetate (1.25 g, 15.23 mmol) aqueous solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and the solvent evaporated. The crude product was purified by column chromatography using 3:22 v/v diethyl ether/n-hexane as an eluent to collect compound D9-3 as a yellow solid (0.21 g, 9%).

(135) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.83 (s, 1H), 7.80 (d, J=8.9 Hz, 2H), 7.68-7.53 (m, 5H), 7.48 (s, 1H), 7.42 (d, J=8.9 Hz, 2H), 7.38-7.22 (m, 6H), 7.19-7.01 (m, 7H), 6.94-6.85 (m, 1H), 4.01-3.79 (m, 4H), 1.76-1.59 (m, 4H), 1.52-1.15 (m, 24H), 0.88 (t, J=6.5 Hz, 6H);

(136) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.65, 151.48, 148.14, 147.13, 147.07, 146.73, 134.42, 131.93, 131.64, 130.50, 129.84, 129.38, 129.04, 128.32, 127.49, 126.91, 124.89, 124.38, 123.55, 123.27, 120.06, 114.52, 113.36, 45.25, 44.45, 31.83, 29.52, 29.48, 29.41, 29.35, 29.23, 29.20, 27.08, 26.98, 24.97, 24.79, 22.63, 14.09;

(137) Anal. calcd for C.sub.51H.sub.63N.sub.5O (%): C, 80.38; H, 8.33; N, 9.19. found: C, 80.40; H, 8.17; N, 9.11.

d) 4-[(N-nonyl-N-phenylhydrazin-2-ylmethyl)diphenylamino]benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-nonylhydrazone (D9)

(138) ##STR00054##

(139) A mixture of D9-3 (0.16 g, 0.21 mmol), rhodanine-3-acetic acid (0.05 g, 0.25 mmol) and ammonium acetate (0.05 g, 0.06 mmol) was refluxed in acetic acid (3.5 mL) for 3 h. Afterwards, water (15 mL) was added and the extraction was done with ethyl acetate. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 1:24 v/v methanol/toluene as an eluent to collect dye D9 as a dark red solid (0.08 g, 41%).

(140) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.72-6.73 (m, 25H), 4.82 (s, 2H), 3.96-3.69 (m, 4H), 1.74-1.49 (m, 4H), 1.44-1.07 (m, 24H), 0.93-0.71 (m, 6H);

(141) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 192.84, 187.16, 176.62, 165.24, 147.08, 134.05, 133.45, 130.09, 129.65, 129.38, 129.04, 127.60, 127.38, 127.07, 126.91, 126.04, 124.89, 124.34, 120.07, 114.53, 114.13, 45.25, 31.83, 29.53, 29.41, 29.23, 27.08, 24.81, 22.64, 14.10;

(142) IR (KBr): v=3481 (OH); 3059, 3030 (aromatic CH); 2951, 2923, 2851 (aliphatic CH); 1708 (C═O); 1577, 1505, 1495 (C═C); 1284 (C═S); 1201, 1187, 1179, 1121, 1103 (C—N); 892, 823 (CH═CH of 1,4-disubstituted benzenes), 747, 722, 693 (CH═CH of monosubstituted benzenes);

(143) Anal. calcd for C.sub.56H.sub.66N.sub.6O.sub.3S.sub.2(%): C, 71.91; H, 7.11; N, 8.99. found: C, 71.83; H, 6.98; N, 8.84.

A3) Preparation of Dyes D10 to D12

Preparation of Dye D10

a) 4-(diphenylamino)benzaldehyde-N-(7-chloroquinolin-4-yl)hydrazone (D10-1)

(144) ##STR00055##

(145) To 4-(diphenylamino)benzaldehyde (1.0 g, 3.66 mmol; corresponds to compound 1 where both radicals R equal phenyl), dissolved in toluene (15 mL), 7-chloro-4-hydrazinoquinoline (1.0 g, 5.16 mmol), dissolved in methanol (30 ml), was added. The mixture was refluxed until the arylaldehyde disappeared (TLC, acetone:n-hexane=7:18). Afterwards, the mixture was cooled to room temperature. Yellow crystals of 9 (1.41 g, 86%), having formed upon standing, were filtered off and washed with a mixture of 2-propanol and n-hexane (1:2). The crude product was used in the next step without additional purification.

b) 4-(diphenylamino)benzaldehyde-N-(4-formyl)phenyl-N-(7-chloroquinolin-4-yl)hydrazone (D10-2)

(146) ##STR00056##

(147) A mixture of D10-1 (1.41 g, 3.15 mmol), 4-fluorobenzaldehyde (1.0 mL, 9.32 mmol) and K.sub.2CO.sub.3 (2.60 g, 18.81 mmol) was refluxed in 20 mL anhydrous DMF under argon atmosphere for 1.5 h. Afterwards, the mixture was cooled to room temperature, water (30 mL) was added and the extraction was done with chloroform. The organic layer was washed with water, dried over anhydrous Na.sub.2SO.sub.4 and filtered. Light orange crystals, having formed after evaporation of the solvent, were filtered off and washed with 2-propanol to give the corresponding arylaldehyde D10-2 (1.13 g, 65%).

(148) .sup.1H NMR (300 MHz, CDCl.sub.3): δ=10.09 (s, 1H, CHO), 8.54-8.47 (m, 2H), 8.08 (d, J=8.5 Hz, 2H), 7.68 (d, J=8.7 Hz, 2H), 7.56 (d, J=8.3 Hz, 2H), 7.32-7.00 (m, 14H), 6.96 (d, J=8.1 Hz, 1H), 6.82 (d, J=1.9 Hz, 1H);

(149) .sup.13C NMR (75 MHz, CDCl.sub.3): δ=190.52, 155.46, 154.81, 149.37, 147.12, 146.38, 139.98, 136.44, 136.07, 131.67, 129.32, 129.13, 128.82, 128.15, 126.70, 125.01, 124.37, 123.52, 122.20, 121.13, 115.43, 101.72;

(150) IR (KBr): v=3065 (aromatic CH); 2957, 2915, 2845, 2742 (aliphatic CH); 1697 (C═O); 1626, 1594, 1492, 1436, 1399 (C═C); 1187, 1174, 1143, 1117, 1105, 1078 (C—N); 857, 837, 805 (CH═CH of 1,4-disubstituted benzenes); 751, 727, 711, 694 (CH═CH of monosubstituted benzenes);

(151) Anal. calcd for C.sub.35H.sub.25ClN.sub.4O (%): C, 76.01; H, 4.56; N, 10.13. found: C, 75.98; H, 4.53; N, 10.11.

c) 4-(diphenylamino)benzaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-(7-chloro-4-quinolin-4-yl)hydrazone (D10)

(152) ##STR00057##

(153) A mixture of D10-2 (0.4 g, 0.72 mmol), rhodanine-3-acetic acid (0.17 g, 0.87 mmol), and ammonium acetate (0.02 g, 0.22 mmol) was refluxed in acetic acid (3 mL) for 50 min. At the end of the reaction, the mixture was cooled to room temperature. Dark orange crystals, having formed upon standing, were filtered off and washed with water, methanol and finally with diethyl ether to give dye D10 (0.4 g, 76%).

(154) .sup.1H NMR (300 MHz, 50% DMSO-d.sub.6/CDCl.sub.3): δ=8.53-8.39 (m, 2H), 7.97 (s, 1H), 7.89 (d, J=8.1 Hz, 2H), 7.80-7.58 (m, 4H), 7.55-7.24 (m, 6H), 7.23-7.01 (m, 7H), 6.97 (d, J=8.4 Hz, 2H), 6.87 (s, 1H), 4.75 (s, 2H);

(155) IR (KBr): v=3408 (OH); 3060, 3034 (aromatic CH); 2923 (aliphatic CH); 1715 (C═O); 1617, 1589, 1523, 1505, 1490 (C═C); 1291 (C═S); 1197, 1176, 1123, 1101, 1076 (C—N); 895, 857, 823 (CH═CH of 1,4-disubstituted benzenes); 753, 729, 696 (CH═CH of monosubstituted benzenes);

(156) Anal. calcd for C.sub.40H.sub.28ClN.sub.5O.sub.3S.sub.2(%): C, 66.15; H, 3.89; N, 9.64. found: C, 66.21; H, 3.90; N, 9.71.

Preparation of Dye D11

a) 1-Phenyl-3-propoxy-1,2,3,4-tetrahydroquinoline-6-carbaldehyde (D11-1)

(157) ##STR00058##

(158) Compound D11-1 was prepared according to T. Malinauskas, J. Stumbraite, V. Getautis, V. Gaidelis, V. Jankauskas, G. Juska, K. Arlauskas, K. Kazlauskas Dyes and Pigments 81 (2009) 131-136.

b) 1-Phenyl-3-propoxy-1,2,3,4-tetrahydroquinoline-6-carbaldehyde-N-phenylhydrazone (D11-2)

(159) ##STR00059##

(160) To compound 011-2 (5.00 g, 17.77 mmol) dissolved in 2-propanol (25 mL), phenylhydrazine (2.31 mL, 21.31 mmol) was added. The mixture was refluxed for 1 h until the arylaldehyde disappeared (TLC, v/v diethylether/n-hexane, 2:3). At the end of the reaction, the mixture was cooled to room temperature. Yellow crystals, having formed upon standing, were filtered off and washed with a mixture of 2-propanol and n-hexane (1:2) to give the corresponding phenylhydrazone 25 (6.5 g, 99%), which was used in the next reaction without further purification.

c) 1-Phenyl-3-propoxy-1,2,3,4-tetrahydroquinoline-6-carbaldehyde-N-(4-formyl)phenyl-N-phenylhydrazone (011-3)

(161) ##STR00060##

(162) A mixture of compound D11-2 (6.5 g, 16.86 mmol), 4-fluorobenzaldehyde (3.14 g, 25.29 mmol), and K.sub.2CO.sub.3 (6.99 g, 50.58 mmol) were refluxed in anhydrous DMF (35 mL) under argon atmosphere for 20 h. After cooling to room temperature, distilled water (30 mL) was added and mixture was extracted with ethyl acetate, dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent was evaporated. The crude product was purified by column chromatography using 2:23 v/v acetone/n-hexane as an eluent to collect compound D11-3 as a yellow solid (5.28 g, 64%).

(163) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.80 (s, 1H), 7.72 (d, J=9.0 Hz, 2H), 7.62 (t, J=7.4 Hz, 2H), 7.52 (t, J=7.4 Hz, 1H), 7.41-7.31 (m, 3H), 7.28-7.09 (m, 9H), 6.68 (d, J=8.6 Hz, 1H), 3.98-3.86 (m, 1H), 3.83-3.73 (m, 1H), 3.61-3.39 (m, 3H), 3.15 (dd, J=15.7, 4.6 Hz, 1H), 2.89 (dd, J=15.9, 7.9 Hz, 1H), 1.65-1.50 (m, 2H), 0.89 (t, J=7.4 Hz, 3H);

(164) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.89, 152.38, 147.35, 145.22, 140.12, 138.77, 131.58, 131.21, 130.14, 129.72, 129.43, 128.79, 128.55, 125.86, 125.60, 125.13, 124.63, 122.17, 115.10, 114.07, 71.33, 70.60, 54.17, 34.40, 23.39, 10.78;

(165) Anal. calcd. for C.sub.32H.sub.31N.sub.3O.sub.2(%): C, 78.50; H, 6.38; N, 8.58. found: C, 78.41; H, 6.52; N, 8.63.

d) 1-Phenyl-3-propoxy-1,2,3,4-tetrahydroquinoline-6-carbaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-ylidenmethyl)phenyl-N-phenylhydrazone (D11)

(166) ##STR00061##

(167) A mixture of compound D11-3 (0.99 g, 2.03 mmol), rhodanine-3-acetic acid (0.46 g, 2.43 mmol) and ammonium acetate (0.05 g, 0.61 mmol) was refluxed in acetic acid (3.0 mL) for 2 h. Afterwards, water (15 mL) was added and the extraction was done with chloroform. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 2:23 v/v methanol/toluene as an eluent to collect dye D11 as a dark red solid (0.81 g, 61%).

(168) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.82-7.05 (m, 17H), 6.72 (dd, J=8.5, 6.2 Hz, 1H), 6.41 (d, J=8.9 Hz, 1H), 4.89 (s, 2H), 4.04-3.89 (m, 1H), 3.89-3.41 (m, 4H), 3.27-2.84 (m, 2H), 1.71-1.52 (m, 2H), 1.03-0.83 (m, 3H);

(169) Anal. calcd for C.sub.37H.sub.34N.sub.4O.sub.4S.sub.2(%): C, 67.05; H, 5.17; N, 8.45. found: C, 67.17; H, 5.31; N, 8.58.

Preparation of Dye D12

a) 1,2,3,3a,4,8b-hexahydro-4-[4-(2,2-diphenylethenyl)phenyl]cyclopenta[b]indole-7-carboxaldehyde (D12-1)

(170) ##STR00062##

(171) Prepared according to published Japanese patent application JP 2010-083767.

b) 1,2,3,3a,4,8b-hexahydro-4-[4-(2,2-diphenylethenyl)phenyl]cyclopenta[b]indole-7-carboxaldehyde-N-phenylhydrazone (D12-2)

(172) ##STR00063##

(173) To compound D12-1 (1.50 g, 3.39 mmol) dissolved in toluene (8 mL) and 2-propanol (4 mL), phenylhydrazine (0.40 mL, 4.08 mmol) was added. The mixture was refluxed for 2.5 h until the arylaldehyde disappeared (TLC, toluene). At the end of the reaction, the mixture was cooled to room temperature. Yellow crystals, having formed upon standing, were filtered off and washed with 2-propanol to give the corresponding phenylhydrazone D12-2 (1.42 g, 79%), which was used in the next reaction without further purification.

c) 1,2,3,3a,4,8b-hexahydro-4-[4-(2,2-diphenylethenyl)phenyl]cyclopenta[b]indole-7-carboxaldehyde-N-(4-formyl)phenyl-N-phenylhydrazone (D12-3)

(174) ##STR00064##

(175) A mixture of compound D12-2 (1.3 g, 2.45 mmol), 4-fluorobenzaldehyde (0.45 g, 3.7 mmol), and K.sub.2CO.sub.3 (1.02 g, 7.34 mmol) were refluxed in anhydrous DMF (25 mL) under argon atmosphere for 5 h (TLC, toluene). After cooling to room temperature, distilled water (30 mL) was added and mixture was extracted with ethyl acetate, dried over anhydrous Na.sub.2SO.sub.4, filtered and solvent was evaporated. The crude product was purified by column chromatography using 2:2:21 v/v acetone/THF/n-hexane as an eluent to collect compound D12-3 as a yellow solid (0.86 g, 55%).

(176) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 9.98 (s, 1H), 7.93 (d, J=8.7 Hz, 2H), 7.74 (d, J=8.9 Hz, 2H), 7.64 (t, J=7.4 Hz, 2H), 7.60-7.50 (m, 2H), 7.50-7.12 (m, 16H), 7.11-6.88 (m, 4H), 4.86-4.66 (m, 1H), 3.96-3.70 (m, 1H), 2.15-1.36 (m, 6H);

(177) .sup.13C NMR (75 MHz, CDCl.sub.3, δ): 190.87, 161.26, 152.46, 148.16, 143.81, 141.28, 140.97, 140.43, 138.88, 136.31, 132.85, 132.33, 131.67, 131.30, 130.96, 130.68, 130.62, 130.26, 129.52, 129.05, 128.62, 128.44, 128.03, 127.85, 127.63, 127.49, 126.44, 122.66, 119.63, 118.53, 114.15, 108.29, 69.10, 45.36, 35.12, 34.10, 24.63; Anal. calcd. for C.sub.45H.sub.37N.sub.3O (%): C, 85.01; H, 5.87; N, 6.61. found: C, 85.25; H, 5.72; N, 6.59.

d) 1,2,3,3a,4,8b-hexahydro-4-[4-(2,2-diphenylethenyl)phenyl]cyclopenta[b]indole-7-carboxaldehyde-N-4-(3-carboxymethyl-4-oxo-2-thioxo-1,3-thiazolidin-5-yliden-methyl)phenyl-N-phenylhydrazone (D12)

(178) ##STR00065##

(179) A mixture of compound D12-3 (0.205 g, 0.32 mmol), rhodanine-3-acetic acid (0.074 g, 0.39 mmol) and ammonium acetate (0.015 g, 0.19 mmol) was refluxed in acetic acid (3.0 mL) for 6.5 h. Afterwards, water (15 mL) was added and the extraction was done with chloroform. The organic layer was dried over anhydrous Na.sub.2SO.sub.4, filtered, and solvent evaporated. The crude product was purified by column chromatography using 47:3 v/v toluene/methanol as an eluent to collect dye D12 as a dark red solid (0.125 g, 48%).

(180) .sup.1H NMR (300 MHz, CDCl.sub.3, δ): 7.74-7.47 (m, 3H), 7.45-7.08 (m, 20H), 7.06-6.80 (m, 6H), 4.95-4.66 (m, 3H), 3.97 (dd, J=7.5, 5.8 Hz, 1H), 2.14-1.71 (m, 6H);

(181) Anal. calcd. for C.sub.50H.sub.40N.sub.4O.sub.3S.sub.2(%): C, 74.23; H, 4.98; N, 6.93. found: C, 74.50; H, 5.11; N, 6.69.

B) Preparation and Characterization of the DSCs

General Methods and Materials

(182) Preparation of the (solid-state) DSCs: A TiO.sub.2 blocking layer was prepared on a fluorine-doped tin oxide (FTO)-covered glass substrate using spray pyrolysis (cf. B. Peng, G. Jungmann, C. Jager, D. Haarer, H. W. Schmidt, M. Thelakkat, Coord. Chem. Rev. 2004, 248, 1479). Next, a TiO.sub.2 paste (Dyesol), diluted with terpineol, was applied by screen printing, resulting in a film thickness of 1.7 μm. All films were then sintered for 45 min at 450° C., followed by treatment in a 40 mM aqueous solution of TiCl.sub.4 at 60° C. for 30 min, followed by another sintering step. The prepared samples with TiO.sub.2 layers were pretreated with 5 mM solutions of the additives 2-(p-butoxyphenyl)acetohydroxamic acid (“ADD3”), 2-(p-butoxyphenyl)acetohydroxamic acid sodium salt (“ADD1”) or 2-(p-butoxyphenyl)acetohydroxamic acid tetrabutylammonium salt (“ADD2”) in ethanol (these additives are described on pages 52 and 53 of WO 2012/001628 A1 as “Example No. 5”, “Example No. 6” and “Example No. 10”, respectively). The electrodes were then dyed in 0.5 mM dye solution in CH.sub.2Cl.sub.2. Spiro-MeOTAD was applied by spin-coating from a solution in DCM (200 mg/mL) also containing 20 mM Li(CF.sub.3SO.sub.2).sub.2N. Fabrication of the device was completed by evaporation of 200 nm of silver as the counter electrode. The active area of the sDSC was defined by the size of these contacts (0.13 cm.sup.2), and the cells were masked by an aperture of the same area for measurements. The current-voltage characteristics for all cells were measured with a Keithley 2400 under 1000 W/m.sup.2, AM 1.5G conditions (LOT ORIEL 450 W). The incident photon to current conversion efficiency's (IPCE) were obtained with an Acton Research Monochromator using additional white background light illumination.

(183) The samples were illuminated with monochromatic light from the quartz monochromator with deuterium lamp. The power of the incident light beam was (2-5).Math.10.sup.−8 W. The negative voltage of −300 V was supplied to the sample substrate. The counter-electrode with the 4.5×15 mm.sup.2 slit for illumination was placed at 8 mm distance from the sample surface. The counter-electrode was connected to the input of the BK2-16 type electrometer, working in the open input regime, for the photocurrent measurement. The 10.sup.−15-10.sup.−12 A strong photocurrent was flowing in the circuit under illumination. The photocurrent J is strongly dependent on the incident light photon energy hν. The J.sup.0.5=f(hν) dependence was plotted. Usually the dependence of the photocurrent on incident light quanta energy is well described by linear relationship between J.sup.0.5 and hν near the threshold (cf. E. Miyamoto, Y. Yamaguchi, M. Yokoyama, Electrophotography 1989, 28, 364 and M. Cordona, L. Ley, Top. Appl. Phys. 1978, 26, 1). The linear part of this dependence was extrapolated to the hν axis and J.sub.p value was determined as the photon energy at the interception point.

(184) The results of the DSCs with varying dyes and additives are given in the following table 1.

(185) TABLE-US-00001 TABLE 1 Photovoltaic performance of sDSCs based on the D1-D12 dyes Dye Additive J.sub.SC [mA cm.sup.−2] V.sub.OC [mV] FF [%] η [%] D1 ADD1 7.34 680 51 2.5 D1 ADD3 6.86 560 57 2.2 D2 ADD1 7.82 760 62 3.7 D2 ADD2 6.9 580 55 2.2 D3 ADD1 7.00 800 64 3.6 D3 ADD2 8.04 660 58 3.1 D4 ADD1 6.51 840 64 3.5 D4 ADD2 7.28 840 62 3.8 D8 ADD1 2.76 740 56 1.1 D8 ADD2 3.42 780 58 1.5 D9 ADD1 5.3 800 74 3.1 D9 ADD2 4.18 760 69 2.2 D11 ADD1 6.08 780 68 3.2 D11 ADD2 6.9 720 66 3.3 D12 ADD1 7.68 680 61 3.2 D12 ADD2 7.71 740 63 3.6