аЯрЁБс>ўџ 68ўџџџ5џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС7 №ПХbjbjUU .7|7|Љџџџџџџl$$$$$$$ ***8b$† ДЖІІ(ЮЮЮЉЉЉ3555555$j ŠœY$ЉЉЉЉЉY‡ $$ЮЮлn‡ ‡ ‡ Љ$Ю$Ю3‡ Љ3‡ Є‡ +:п,$$Юš p&YыєР Š*Б ж  „0Д &‡ &‡ 8<t,$$$$йA Novel Approach Towards Low Optical Band Gap Polysquaraines A. Ajayaghosh* and J. Eldo Photochemistry Research Unit, Regional Research Laboratory, CSIR, Trivandrum 695 019, India * Author to whom correspondence should be addressed. Fax: +91 471 490 186, E-mail: aajayaghosh@rediffmail.com Supporting Information Experimental Section Materials The solvents and reagents were purified and dried by usual methods prior to use. Pyrrole, dodecylbromide and 3,4-dihydroxy-3-cyclobutene-1,2-dione were purchased from Sigma-Aldrich. Measurements All melting points were determined with a Mel-Temp-II melting point apparatus and are uncorrected. 1H and 13C NMR were measured on a 300 Mz Bruker Avance DPX spectrometer. IR spectra were recorded on a Nicolet Impact 400D infrared spectrophotometer. High-resolution mass spectra were recorded on a JEOL JM AX 505 HA mass spectrometer at the Radiation Laboratory, University of Notre Dame. The UV-Vis-NIR spectra were recorded on Shimadzu UV-3101 PC NIR Scanning spectrophotometer. The molecular weight of 3a was determined on a Waters GPC system using polystyrenes as standard and THF as eluent at a flow rate of 2 mL/ min. Thermogravimetric analysis of 3a-c were carried out on a Shimadzu TGA-50H thermal analyser. X-ray diffraction patterns were obtained on a Phillips diffractometer using Ni filtered Cu K( radiation. Intrinsic conductivities were measured using pressed pellets on a Kiethley model 6517A Electrometer. Procedures Synthesis of polysquaraines 3a-c and the model squaraine dye 4 Preparation of bispyrroles 1a-c A suspension of sodium hydride (30 mmol) in THF was added slowly to a solution of the corresponding 2,5-bis (alkyloxy)-1,4-bis (benzyl) phosphonate (5 mmol) and the respective N-alkylpyrrole-2-carboxaldehyde (10 mmol) in THF. After refluxing for 10 h the highly fluorescent reaction mixture was cooled and THF was removed under reduced pressure to give a solid residue. This residue was suspended in water and extracted with dichloromethane. The organic layer was washed with brine, dried over MgSO4 and concentrated to give a crude product, which was further purified by several precipitations from dichloromethane solution with methanol. The spectral data of 1a-c after recrystallization from a mixture of dichloromethane/petroleum ether were in agreement with their structures as illustrated below. 1a: yield 64%, mp. 91-92 oC; IR (KBr) (max 2931, 2863, 1656, 1628, 1509, 1490, 1392, 1360, 1295, 1094, 962 cm-1; 1H NMR (300 MHz, CDCl3) ( 7.09 (d, J=15.56 Hz, 2H), 7.06 (d, J=15.66 Hz, 2H), 6.95 (s, 2H), 6.66 (m, 2H) 6.48 (m, 2H), 6.14 (t, J=2.94 Hz, 2H), 4.01 (t, J=7.0 Hz, 4H), 3.95 (t, J=6.63 Hz, 4H), 1.82-1.24 (m, 64H), 0.87 (t, J=6.7 Hz, 12H); 13C NMR (75.4 MHz, CDCl3), ( 150.91, 132.09, 126.54, 122.40, 121.43, 117.79, 111.19, 108.13, 106.44, 69.45, 47.08, 31.90, 31.57, 29.64, 29.45, 29.34, 29.28, 26.87, 26.28, 22.67, 14.10; HRMS calcd for C58H96N2O2 (M+): 852.7472, found 852.7468. 1b: yield 48%; mp 85-86 oC; IR (KBr) (max 2927, 2857, 1543, 1496, 1461, 1336, 1288, 1206, 1046, 955 cm-1; 1H NMR (CDCl3) ( 7.03 (d, J=16.12 Hz, 2H), 6.91 (d, J=16.3 Hz, 2H), 6.89 (s, 2H), 6.56 (s, 2H), 6.40 (m, 2H), 6.05 (t, J=3.13 Hz, 2H), 3.88 (t, J=7.16 Hz, 4H), 3.80 (s, 6H), 1.69 (t, 4H), 1.25-1.17 (m, 36H), 0.80 (t, J=6.82 Hz, 6H); 13C NMR (CDCl3) ( 151.40, 131.85, 126.53, 122.40, 120.79, 117.71, 109.56, 108.26, 106.82, 56.34, 47.08, 31.91, 31.59, 29.62, 29.37, 29.31, 26.91, 22.74, 14.12; HRMS calcd for C44H68N2O2 (M+): 656.5281, found 656.5256. 1c: yield 63%; mp 140-142 oC; IR (KBr) (max 2949, 2868, 1462, 1417, 1327, 1197, 1039, 1012, 954, 707 cm-1; 1H NMR (CDCl3) ( 7.08 (d, J=16.26 Hz, 2H), 7.00 (d, J=16.30 Hz, 2H), 6.56 (s, 2H), 6.91 (s, 2H), 6.42 (m, 2H), 6.09 (t, J=2.75 Hz, 2H), 3.96 (t, J=6.27 Hz, 4H), 1.74 (t, 4H), 3.63 (s, 6H), 1.50 (m, 4H), 0.94 (t, J=7.31 Hz, 6H); 13C NMR (CDCl3) ( 150.93, 132.87, 126.56, 123.44, 121.46, 117.56, 110.95, 108.23, 106.63, 69.12, 34.15, 31.66, 19.47, 13.91; HRMS calcd for C28H36N2O2 (M+): 432.2777, found 432.2770. Preparation of polysquaraines 3a-c The bispyrroles 1a-c (0.15 mmol) and squaric acid (0.15 mmol) in butanol/benzene (1:3, 40 mL) was refluxed for 12-20 h under the azeotropic removal of water. The reaction mixture was cooled, filtered and the filtrate was concentrated under reduced pressure. The resultant dark green residue was dissolved in dichloromethane and the product was precipitated with light petroleum ether. After three reprecipitation with petroleum ether and subsequent washing with diethylether, 3a-c were obtained in 69-75% yields. 3a: yield 69%, IR (KBr) (max 2921, 2859, 1620, 1489, 1359, 1284, 1091, 954 cm-1; 1H NMR (CDCl3, 300 MHz) ( 7.5-7.8 (m, broad, vinylic), 6.8-7.01 (m, broad, aromatic), 4.78 (s, broad, NCH2), 3.62-3.92 (m, NCH2 & OCH2), 1.22-1.86 (m, CH2, 64H), 0.84 (t, CH3, 12H); 13CNMR (CDCl3, 75.4 MHz) ( 14.12, 22.7, 26.28, 26.53, 29.39, 29.46, 29.70, 31.94, 46.71, 69.33, 113.58, 113.92, 130.5, 151.9, 161.76, 177.79; Elemental analysis calculated for a repeating unit of C62H94N2O4.H2O: C, 78.43; H, 10.19; N, 2.95. Found: C, 77.72; H, 10.31; N, 2.77. 3b: IR (KBr) (max 2923, 2860, 1621, 1486, 1359, 1291, 1088, 950 cm-1; Elemental analysis calculated for a repeating unit of C48H66N2O4.H2O: C, 76.55; H, 9.1; N, 3.72. Found: C, 76.40; H, 9.37; N, 3.66. 3c: IR (KBr) (max 2950, 1612, 1493, 1342, 1274, 1101, 953 cm-1. Elemental analysis calculated for a repeating unit of C32H34N2O4.H2O: C, 72.74; H, 6.86; N, 5.3. Found: C, 72.92; H, 6.86; N, 5.57. The structure of 3c is established via the structure of 4. Preparation of the Model Compound 4 Compound 4 was prepared under high dilution as follows. The bispyrrole 1c (0.4 mmol) and squaric acid (0.2 mmol) were dissolved in butanol/benzene (1:3, 80 mL) and the reaction mixture was refluxed under azeotropic conditions. The reaction was monitored by recording the absorption spectrum at different intervals. Reaction was stopped when the absorption bands corresponding to the higher homologues started appearing. The reaction mixture was cooled, filtered and the benzene was removed under reduced pressure to give a viscous solution. The product was precipitated by adding light petroleum ether and the unreacted bispyrrole monomers were removed using repeated washings with petroleum ether and diethyl ether to get 4 in 38% yield. 4: IR (KBr) (max 2930, 1620, 1440, 1352, 1283, 1096, 939 cm-1; 1H NMR (CDCl3) ( 7.77 (s, 2H), 7.4 (s, broad, 2H), 7.17-7.10 (m, 6H), 6.92 (m, 6H), 6.63 (s, 2H), 6.51(s, 2H), 6.16 (s, 2H), 4.22 (s, 6H), 4.04 (s, 6H), 3.48-3.67 (m, 8H), 1.85 (s, broad, 8H), 1.63 (m, 8H), 1.03 (m, 6H); HRMS calcd for C60H70N4O6 (M+): 942.5295, found 942.5327. Anal. calcd for C60H70N4O6.H2O: C, 74.96; H, 7.55; N, 5.82. Found: C, 74.97; H, 7.96; N, 6.07. PAGE 1 PAGE 4 <>?Z[Й&()U_#%‰Š’"$ЗЛQ R У Ю . о п ! 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