Synthetic Metals 99 1999.

916

Visible-emitting polyw 3 ,4 -dialkoxycarbonyl-2X-hydroxy-1,1X :5X ,1Y-terphenyl-4,4Y-ylene/ x

X X

Ken O. Annan a , Ullrich Scherf

a

b, )

, Klaus Mullen

The Chemistry Department, Queen Mary and Westfield College, Uniersity of London, Mile End Road, London E1 4NS, UK b Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany Received 20 July 1998; revised 1 September 1998; accepted 29 September 1998

Abstract The synthesis and characterisation of a series of visible-emitting polyphenylenes composed of para-quarterphenylene segments interconnecting at meta-phenylene junctions are presented. The polymers were obtained by nickel catalysed homocoupling of the corresponding 1,5-bis4-bromophenyl.-2-hydroxy-3,4-dialkoxycarbonylbenzenes. Structural characterisation by microanalysis, FT-IR, 1 H and 13C NMR, and UVVisible spectroscopy agree with the proposed structure of the polymers, with no obvious indication if there are structural defects. Fluorescence analysis of a methylene chloride solution of two materials indicated maximum emission lmax s 463 and 411 nm, respectively. in the visible spectrum. q 1999 Elsevier Science S.A. All rights reserved.
Keywords: Polyphenylene; Luminescence; Resonance stabilisation; p-Electron delocalisation

1. Introduction A perennial problem that plagues the synthesis and characterisation of high molecular weight, and regiochemically pure polyphenylenes is the insolubility and intractability of the materials as a consequence of the rigid rod backbone structure w13x. Most conventional synthesis of polyphenylenes have thus resulted in unprocessable and infusible materials of low molecular weight that are difficult to characterise unequivocally w1,3x. In recent years, a great deal of research effort has concentrated on developing routes to polyphenylenes that incorporate groups which provide solubility and processability, and concomitantly high molecular weight material of regioregular final structure w48x. This has facilitated the synthesis of polyphenylene materials of remarkably interesting properties, such as extended p-electron delocalisation and high thermal stability in the neutral state which promise considerable technological applications especially in the fabrication of electroluminescent devices w7x. Traditionally, polyphenylenes containing meta-phenylene units have not attracted a great deal of interest possibly due to the interrupted conjugation along the backbone. Although not conclusively characterised, an unsubstituted

poly meta-phenylene. has been reported to emit blue light in the solid state w9x, and an alkoxy substituted poly metaphenylene. has been shown to give emission that trails into the visible spectrum, and in this way, imparts a faint purple luminescence to the polymer w10x. In this study, the synthesis and characterisation of a series of polyw3X ,4X-dialkoxycarbonyl-2X-hydroxy-1,1X :5X ,1Yterphenyl-4,4Y-ylene.xs together with a 2-methoxy analogue comprising para-quarterphenylene units Fig. 1. connected by meta junctions are presented. The polymers were obtained via nickel catalysed polycondensation of the corresponding 1,5-bis4-bromophenyl.-2-hydroxy-3,4-dialkoxycarbonylbenzenes, according to the method of Yamamoto et al. w11x. The alkoxy substituents facilitate a high degree of solubility of the polymers in conventional organic solvents. 2. Results and discussion The appropriate monomers comprising of the 1,5bis4-bromophenyl.- 2 -hydroxy- 3,4 -dialkoxycarbonylbenzenes 8ad. were obtained via the preparation of the 1,4-diketone 4 from a Mannich type reaction, followed by cyclodehydration in the presence of polyphosphoric acid to give the furan 5. The 2,5-bis4-bromophenyl.furan 5. is then reacted with the corresponding acetylene dienophile 6 in the presence of AlCl 3 to form the DielsAlder product

Corresponding author.

0379-6779r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved. PII: S 0 3 7 9 - 6 7 7 9 9 8 . 0 0 1 7 7 - 5

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K.O. Annan et al. r Synthetic Metals 99 (1999) 916

X X X Fig. 1. An illustration of the polyw3 ,4 -dicalkoxycarbonyl-2 -hydroxyX X Y Y . x 1,1 :5 ,1 -terphenyl-4,4 -ylenes structure incorporating para-quarterphenylene units and meta-phenylene junctions.

7 which undergoes facile acid catalysed re-arrangement at elevated temperatures; as illustrated in Scheme 1 to give compounds based on structure 8 w12,13x. A 2-methoxy analogue 9 was realised by etherification of compound 8b with methyl iodide Scheme 2.. The preparative details and structural analysis of the monomers are described in Section 3. Figs. 2 and 3 give the single crystal X-ray structures of the cycloadduct 7 and the re-arranged benzene derivative 8b, respectively. Compound 7 crystallises in the monoclinic space group C 2 , while compound 8b crystallises in monoclinic space group P 2rn. Both compounds deviate significantly from planarity, but in addition to that, compound 7 shows severe angle strain leading to distortion of the endoxide ring. This is relieved in the re-arranged derivative 8b, with the substituents around the central benzene ring evenly spaced at ca. 1208. The relief of steric strain together with a gain of resonance stabilisation energy thus, provides the driving force for the observed re-arrangement.

The respective monomers were polycondensed via the nickel catalysed homocoupling reaction of Yamamoto et al. w11x Scheme 3.. The reaction is reported to tolerate the presence of several functionalities. Initial room temperature polycondensation of 8 regenerated the un-reacted monomer 8, however, good results were obtained at 608C over 16 h. Details of the reaction protocol is described in Section 3. The IR spectra of 10 showed a characteristic band at 1717 cmy1 10b., 1728 cmy1 10a., 1737 cmy1 10c., and 1738 cmy1 10d., respectively, which is attributed to the C5O of the ester groups. The band at 1397 cmy1 indicate the presence of OH bending vibration of the phenolic group. The ether derivative 10d displayed bands at 2864 and 1074 cmy1 due to the aryl ether group. The good solubility of the polymers in conventional organic solvents such as THF, methylene chloride, toluene, and dimethylformamide DMF. allowed their characterisation by solution analytical techniques. The 1 H NMR and spectrum of the high molecular weight polymer 10b showed a signal at d 11.62 which exchanged with D 2 O ascribed to the hydroxyl group, signals in the d 7.696.78 indicated the presence of the phenylene groups. Polymer 10d which is devoid of the signal due to the hydroxyl group, showed instead a distinct singlet at d 3.58 due to the methoxy group. The carbon-13 spectrum of polymer 10b displayed signals at d 169.98 and 168.54 due to the carbonyl groups, signals in the aromatic region ascribe to the carbons of the phenylene groups, and two resonance peaks at d 62.82 and 62.01 assigned to the methylene carbons of the ester groups. This spectrum is typical of the spectrum of the other polymers 10a, 10c, 10d. in the series. The spectrum of polymer 10d showed an additional signal at d 14.28 due to the methoxy carbon.

Scheme 1. An illustration of the acid catalysed re-arrangement of 1,4-substituted diaryl-7-oxabicyclow2.2.1x2,3-dicarboxylate adduct to 4,6-substituted diaryl 3-hydroxyphthalates.

K.O. Annan et al. r Synthetic Metals 99 (1999) 916

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Scheme 2. A schematic illustration of the route to the monomers used in polycondensation.

Elemental analysis showed the presence of a small amount of Br ca. less than 1 brominer20 monomer units.. Table 1 lists weight and number of average molecular weights M w , M n ., molecular weight distribution M w rMn ., and number of average degree of polymerisation of the polymers obtained by gel permeation chromatography GPC. in THF relative to polystyrene standards.

All the polymers gave a monomodal curve with polydispersity indices ranging between 1.413.55. The table shows that polymers 10b and 10d gave the highest molecular weight materials, however, there is no clear pattern to suggest why this happened. The optical absorption spectra of the polymers 10b and 10d measured in methylene chloride are given in Figs. 4 and 5, respectively, and Table 2 lists the absorption and

Fig. 2. X-ray crystallographic structure of the cycloadduct 7..

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Fig. 3. X-ray crystallographic structure of the re-arranged benzene derivative 8b..

molar absorptivity data of the polymers 10ad. Polymers 10a and 10d showed one absorption band at 286 and 301 nm, respectively, and the remaining polymers of the series displayed two absorptions in the UVVisible region of the spectrum. The polymers display a yellowishrgreen fluorescence in solution. The etherification of the phenolic OH group in polymer 10d did not particularly improve the emission intensity. The emission spectrum of polymer 10d recorded in methylene chloride is given in Fig. 6 and displays an emission band centered at 411 nm. A comparison of the UVVisible absorption data of the polymers described here, with that of poly para-phenylene. l max s 379 nm. w1x indicates a decrease in lmax of between 40100 nm in respect of polymers 10ad, representing a considerable

shift in bandgap due to a break in conjugation associated with the meta-phenylene junctions along the polymer chain.

3. Experimental 3.1. Equipment and reagents All air sensitive manipulations were performed under Schlenck-line techniques in a M Braum MB150B-G drybox, maintained under positive argon pressure from a MB 30G gas purging system. Other procedures requiring inert conditions were carried out in glassware dried in an oven overnight then purged under a stream of argon. A 60 ml syringe equipped with a 12 gauge stainless steel needle

Scheme 3. A schematic representation of the polycondensation regimen.

K.O. Annan et al. r Synthetic Metals 99 (1999) 916 Table 1 Molecular weight data of polymers determined by GPC in THF relative to polystyrene standard Material Polymer 10a. Polymer 10b. Polymer 10c. Polymer 10d. Mw 4073 20 830 3561 12 668 Mn 1669 5867 2523 6232 M w r Mn 2.44 3.55 1.41 2.03 DPn 5 15 5 16

13

was used to transfer sensitive reagents between flasks. HPLC grade solvents were used without further purification, reagents unless otherwise stated were purchased from either Aldrich Chemical or Lancaster. Analytical thin layer chromatography was performed using ready-made plates, SIL GrUV254 from Macherey-Nagel. Flash chromatography was carried out with glass columns, using Fluka silica gel 60; particle size 0.040.063 mm 230400 mesh ASTM.. Solutions of compounds obtained from extraction procedures, were unless otherwise specified dried over anhydrous magnesium sulphate. 1 H and 13 C NMR measurements with shifts relative to internal TMS, were recorded on Varian Gemini 200, Bruker AC-300, and AC-500 with proton operating frequencies of 200, 300, and 500 MHz, respectively, and a corresponding carbon-13 frequencies of 50, 75, and 125 MHz. EIrFD mass spectra were obtained from Trio 200 Quadrupol, and VG ZAB 2-SE-FPD spectrometers, respectively, and MALDI-MS analysis were determined on a Bruker-reflex-TOF FM0405 spectrometer. IR spectra were taken using KBr mulls pressed into pellets or thin films cast onto NaCl plates as transmission windows, on a Nicolet 320 FT-IR spectrometer. Optical absorption measurements were measured on a Perkin-Elmer Lambda 15 UVVis spectrophotometer, fluorescence measurements were taken on a SPEX-USA Double Monochromator, Fluorolog 2 F212 spectrometer. Elemental analysis were obtained from facilities at Institut fur Organische Chemie, Johannes Gutenberg Universitat, Mainz, Germany. Melting points are uncorrected, and were

Fig. 5. Optical absorption spectrum of polymer 10d..

determined in melting point tubes on a Buchi-Melting point apparatus. Thermogravimetric measurements were carried out on Mettler TA 3000, and tandem GPC studies were performed on Waters GPC, equipped with PL-Gel columns. 10m , 10 3, 10 5, 10 6 A Synthesis of Mannich salt (2). Dry dimethylamine hydrochloride 6.63 g, 0.082 mol., powdered paraformaldehyde 2.50 g, 0.083 mol. and 4-bromoacetopheneone 12.4 g, 0.062 mol. were placed in a 100 ml round bottomed flask attached to a reflux condenser. Ninety five percent ethanol 10 ml. to which concentrated HCl 0.13 ml. had been added, was added. The resulting mixture was refluxed an a water bath for 2 h. The reaction mixture which had become clear and homogeneous was transferred to a 250 ml wide-mouthed conical flask, and while still warm, acetone 50 ml. was added. The mixture was allowed to cool to room temperature, and left in a refrigerator overnight. The white crystals were filtered off at the pump, washed with acetone 3 ml., and dried for 6 h at 408C, to give a crude yield of the Mannich salt 2. 15.42 g, 85%.. MS: mrz s 293 100, Mq. FD, C 11 H 15 ONBrCl requires 292.5.. 1 H CDCl 3 , 306 K, 200 MHz.: d 7.88 2H, d, J s 8 Hz., 7.74 2H, d, J s 8 Hz., 4.75 4H, s., 3.59 2H, s., 2.99 6H, s., 2.78 1H, s.. Synthesis of Mannich base (3). The Mannich salt 2. from above was placed in a 250 ml round bottomed flask, and aqueous solution of KOH 2.96 g, 0.053 mol., was
Table 2 Absorption and emission data of polymers and their respective monomers Materials Optical absorption, lma x nm. 286 292 356 287 357 301 Extinction coefficient, ) M 1 cmy 1 . 5833 6473 5833 7244 7559 12 563 Emission, lma x nm.

Polymer 10a. Polymer 10b. Polymer 10c. Polymer 10d. Fig. 4. Optical absorption spectrum of polymer 10b..

463

411

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K.O. Annan et al. r Synthetic Metals 99 (1999) 916

Fig. 6. Emission spectrum of polymer 10d..

added. The resulting mixture was stirred at room temperature for 1 h. The white solid was filtered at the pump washed with water, and dried at 508C over 10 h to give the Mannich base 3. 12.87 g, 95%., m.p. 68708C. MS: mrz s 257 100, Mq. FD, C 11 H 14 ONBr requires 256.. IR-KBr.: n s 3096, 3072, 3024, 2981, 2946, 2908, 2861, 2817, 2787, 2768, 1681, 1585, 1568, 1459, 1446, 1413, 1398, 1382, 1277, 1267, 1240, 1203, 1070, 1043, 1035, 1010, 983, 869, 843, 793, 777 cmy1 . 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 7.81 2H, d, J s 8 Hz., 7.60 2H, d, J s 8 Hz., 3.09 2H, t, J3,2 s 8 and 6 Hz., 2.73 2H, t, J2,3 s 6 and 8 Hz., 2.27 6H, s.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 198.80 1C, C5O., 136.20, 132.82, 130.20, 128.75, 54.62, 46.01, 37.65. Synthesis of 1,4-bis(4-bromophenyl)buta-1,4-dione (4). Sodium cyanide 0.39 g, 6 mmol. and dry DMF 15 ml. were placed in a 100 ml three-necked round-bottomed flask equipped with a magnetic stirring bar, a reflux condenser fitted with KOH guard-tube, a cylindrical funnel with pressure equalising tube, and an argon inlet tube. The content of the flask was heated to 358C with stirring on an oil bath, and 4-bromobenzaldehyde 8.60 g, 46 mmol. in dry DMF 15 ml. was added during 1.5 h. The resulting mixture was stirred at the same temperature 358C. for a further 0.5 h. Then, the Mannich base 3. 11.84 g, 46 mmol. in dry DMF 15 ml. was dropped with stirring at the same temperature during 2 h. The resulting reaction mixture was stirred at the same temperature 358C. for a further 1 h, then it was poured into water 100 ml., and acidified with dilute 1 N. HCl, to remove any unreacted Mannich base. The mixture was transferred to a separatory funnel, and extracted three times with 50 ml portions of dichloromethane. The organic layer was washed with dilute NaHCO 3 solution, and dried over MgSO4 . The solvent was removed on the rotary evaporator, and the resulting white solid was recrystallised from acetic acid to yield pure the 1,4-bis(4-bromophenyl) buta-1,4-dione 10.38 g, 56%. w14x as light white platelets. M.p. 1831848C. Anal. calcd. for wC 16 H 12 O 2 Br2 x required: C s 48.49%, H s 3.03%, Found: C s 48.37%, H s 2.95%. MS: mrz s 396.3

100, Mq. FD, C 16 H 12 O 2 Br2 requires 396.. IR-KBr.: n s 3096, 3072, 3048, 2948, 2897, 1671, 1640, 1629, 1610, 1588, 1568, 1545, 1484, 1405, 1394, 1364, 1327, 1303, 1280, 1192, 1182, 1104, 1075, 1003, 979, 849, 839, 785, 771, 659, 563, 521, 459, 452 cmy1 . 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 7.89 4H, d, J s 9 Hz., 7.62 4H, d, J s 9 Hz., 3.41 4H, s.. 13 C NMR CDCl 3 , 306K 75 MHz.: d 196.77 2C, C5O., 135.79, 131.77, 129.70, 128.15, 26.34. (I) Synthesis of 2,5-bis(4-bromophenyl)furan (5). 1,4Bis4-bromophenyl. buta-1,4-dione 1.98 g, 5 mmol., and polyphosphoric acid 4 g. were placed in a 100 ml twonecked round bottomed flask. The resulting mixture was heated at 1608C with stirring for 1.5 h, then crushed ice 50 g. was added. The crystalline furan was filtered off by suction, and recrystallized from ethanol to give pure product 5. 0.94 g, 50%.. (II) Synthesis of 2,5-bis(4-bromophenyl)furan (5). 1,4Bis4-bromophenyl.buta-1,4-dione 1.98 g, 5 mmol., and polyphosphoric acid 2.5 g. were placed in a 100 ml two-necked round-bottomed flask, and acetic anhydride 38 ml. was added. The resulting mixture was stirred at room temperature overnight. The reaction mixture was subsequently poured into an icerwater mixture, and stirred for 2 h. Then, the crystalline furan was subsequently filtered off at the pump, and recrystallised from ethanol to give pure product 5. 1.71 g, 90%., m.p. 2022038C Lit. w15x, m.p. 2012028C, 82%.. MS: mrz s 378.2 100, Mq. FD, C 16 H 12 OBr2 requires 378.. IR-KBr.: n s 3128, 3052, 1910, 1579, 1480, 1473, 1448, 1407, 1346, 1280, 1108, 1076, 1021, 1007, 926, 840, 827, 793, 722, 716, 670, 628, 497, 476 cmy1 . 1 H NMR CDCl 3 , 306 K 200 MHz.: d 7.59 4H, d, J s 8 Hz, H-3,3X ,3Y and 3Z ., 7.53 4H, d, J s 8 Hz., 6.73 2H, s.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 153.20, 132.40, 129.99, 125.82, 121.96, 108.40. The preparative route is a general procedure and is thus described for the preparation of 1,5-bis(4-bromophenyl)2-hydroxy-3,4-diethoxycarbonylbenzene (8b). Typically, a solution of 2,5-bis4-bromophenyl. furan 5. 4 g, 0.011 mol. in dichloromethane 13 ml. was added via 60 ml syringe with a size 12 gauge needle to a stirred mixture of AlCl 3 2.93 g, 0.022 mol. and diethylacetylene dicarboxylate 3.13 g, 0.022 mol. in dichloromethane 85 ml., both solutions being cooled to y208C before mixing. Stirring was continued at the same temperature for 1 h, and the reaction was followed by TLC. The reaction flask was lifted off the cooling bath, and stirring was continued for a further 1 h at room temperature, then water was added to the reaction mixture, and the aqueous mixture was transferred to a separatory funnel. The phases were separated, and the organic phase was washed with water then dried over Na 2 SO4 . The solvent was evaporated off in vacuo, and the residue was triturated with petroleum ether to give a cream coloured solid, which was recrystallised from ethylacetaterpetroleum ether to give pure product 8b.

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4.91 g, 86%., m.p. 1641668C. Anal. calcd. for wC 22 H 16 O5 Br5 x required: C s 50.77%, H s 3.08%, Br s 30.77%. Found: C s 48.81%, H s 2.95%, Br s 34.69%. MS: mrz s 519.7 100, Mq. FD, C 22 H 16 O5 Br2 requires 520.. IR-KBr.: n s 3440, 3104, 3008, 2960, 1712, 1683, 1635, 1620, 1585, 1488, 1435, 1401, 1354, 1313, 1305, 1296, 1278, 1242, 1227, 1201, 1192, 1172, 1152, 1070, 1043, 1009, 985, 841, 827, 805 cmy1 . Optical absorption: lmax s 257 nm s 7513 My1 cmy 1 ., 301 nm s 4656 My1 cmy 1 .. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 7.50 7, m., 7.22 2H, d, J s 8 Hz., 3.95 3H, s., 3.65 3H, s.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 170.20 2C, C5O., 158.80, 145.95, 137.75, 131.85, 130.01, 129.30, 53.80, 52.31. 1,5-Bis ( 4-brom ophenyl ) -2-hydroxy-3,4-diethoxy carbonylbenzene (8b). 3.68 g, 61%. m.p. 1401428C. Anal. calcd. for wC 24 H 20 O5 Br2 x required: C s 52.56%, H s 3.65%, Br s 29.20%. Found: C s 51.79%, H s 3.71%, Br s 26.76%. MS: mrz s 548.1 100, Mq. FD, C 24 H 20 O5 Br2 requires 548.. IR-KBr.: n s 3432, 3104, 2992, 2981, 1725, 1676, 1490, 1465, 1452, 1421, 1388, 1376, 1363, 1340, 1321, 1296, 1278, 1252, 1230, 1183, 1168, 1128, 1095, 1072, 1058, 1026, 1009, 826, 836, 825, 811, 778, 761, 740, 721 cmy1 . Optical absorption: lmax s 241 nm s 8383 My1 cmy 1 ., 332 nm s 1877 My1 cmy1 .. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 11.63 1H, s, D 2 O exchanged, OH., 7.50 7H, m., 7.23 2H, d, J s 8 Hz., 4.43 2H, q, J16, 17 s 8 Hz., 4.08 2H, q, J19, . . 20 s 8 Hz , 1.38 3H, t, J17, 16 s 6 and 8 Hz , 1.06 3H, t, J19, 20 s 6 and 8 Hz.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 169.88 1C, C5O., 168.25 1C, C5O., 158.86, 145.57, 137.31, 135.62, 134.73, 133.60, 132.09, 131.46, 129.49, 123.67, 122.67, 122.51, 110.27, 96.59, 63.13, 61.79, 14.26. 1,5-Bis ( 4-bromophenyl ) -2-hydroxy-3,4-dipentoxy carbonylbenzene (8c). 0.32 g, 46%., m.p. 72748C. Anal. calcd. for wC 30 H 32 O5 Br2 x required: C s 56.96%, H s 5.06%, Br s 25.32%, Found: C s 57.32%, H s 5.16%, Br s 23.36%. MS: mrz s 632.3 100, Mq . FD, C 30 H 32 O5 Br2 requires 632.. IR-KBr.: n s 3432, 3040, 3032, 2956, 2937, 2906, 2870, 2858, 1734, 1673, 1454, 1440, 1424, 1403, 1393, 1382, 1341, 1301, 1283, 1257, 1247, 1229, 1194, 1127, 1012, 989, 836, 832, 768, 746 cmy1 . Optical absorption: lmax s 240 nm s 12 903 My1 cmy1 ., 334 nm s 3495 My1 cmy 1 .. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 11.64 1H, s, D 2 O exchanged., 7,50 7H, m., 7.23 2H, d, J s 8 Hz., 4.36 2H, t, J16, 17 s 6 Hz., 3.98 2H, t, J22, 23 s 6 Hz., 1.73 2H, m., 1.420.83 16H, aliphatics.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 169.82 1C, C5O., 168.14 1C, C5O., 158.54, 138.24, 137.19, 135.43, 134.52, 131.34, 122.37, 110.12, 67.49, 66.11, 28.17, 22.55, 14.28. 1,5-Bis ( 4-bromophenyl) -2-hydroxy-3,4-dihexyloxy carbonylbenzene (8d). 1.19 g, 67%.. m.p. 70718C. Anal. calcd. for wC 32 H 36 O5 Br2 x requires: C s 58.18%, H s 5.46%, Br s 24.24%. Found: C s 57.28%, H s 5.46%, Br s 24.11%. MS: mrz s 660.2 100, Mq . FD,

C 32 H 36 O5 Br2 required 660.. IR-KBr.: n s 3464, 3072, 2957, 2923, 2871, 2856, 1737, 1673, 1493, 1471, 1456, 1443, 1423, 1403, 1385, 1351, 1337, 1304, 1263, 1224, 1197, 1182, 1160, 1127, 1072, 1064, 1011, 987, 836, 821, 744, 728, 483 cmy1 . Optical absorption: l max s 257 nm s 8483 My1 cmy 1 ., 335 nm s 2515 My1 cmy 1 .. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 11.68 1H, s, D 2 O exchanged, OH., 7.48 7H, m., 7.23 2H, d, J s 8 Hz., 4.36 2H, t, J16, 17 s 6 Hz., 3.99 2H, t, J23, 24 s 6 Hz., 1.70 2H, m., 1.34 14H, m., 0.90 6H, m.. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 170.03 1C, C5O., 168.38 1C, C5O., 158.90, 138.55, 137.32, 135.67, 134.78, 131.26, 122.66, 122.56, 110.35, 67.42, 66.24, 31.88, 28.81, 28.66, 25.98, 25.91, 22.96, 14.44. 1,5-Bis ( 4-brom ophenyl ) -2-m ethoxy-3,4-diethoxy carbonylbenzene (9). 1,5-Bis4-bromophenyl.-2-hydroxy3,4-diethoxycarbonylbenzene 8b. 1.00 g, 1.8 mmol. was placed in a 100 ml two-necked round-bottomed flask, N-N X-dimethylacetamide 10 ml. was added. Ammonium tetramethylchloride 0.02 g, 0.18 mmol., K 2 CO 3 0.5 g, 3.6 mmol., and methyl iodide 0.398 g, 2.8 mmol. were subsequently added. The resulting mixture was stirred at 808C overnight. Then the reaction mixture was poured into water 100 ml., and the aqueous mixture was extracted with ether. The ethereal extract was washed twice with water, then 2 N HCl 50 ml., and dried over MgSO4 . Ether was removed under vacuum to leave a brown gum which was purified by chromatography dichloromethanerpetroleum ether 1:1. to yield pure product 9. 0.95 g, 94%.. M.p. 1071088C. Anal. calcd. for wC 25 H 22 O5 Br2 x required: C s 53.38%, H s 3.92%, Br s 28.47%, Found: C s 53.50%, H s 3.99%, Br s 27.75%. MS: mrz s 562.0 100, Mq. FD, C 25 H 22 O5 Br2 required 562., IR-KBr.: n s 3088, 2985, 2976, 2938, 2864, 1739, 1737, 1725, 1590, 1494, 1460, 1440, 1415, 1389, 1377, 1368, 1340, 1301, 1280, 1259, 1234, 1202, 1186, 1176, 1169, 1145, 1111, 1097, 1074, 1056, 1032, 1009, 869, 836, 828, 804, 762, 743, 734, 536 cmy1 . Optical absorption: lmax s 256 nm s 9394 My1 cmy 1 .. 1 H NMR CD 2 Cl 2 , 306 K, 200 MHz.: d 7.55 6H, t, J s 4 and 2 Hz., 7.40 1H, s., 7.23 2H, d, J s 10 Hz., 4.38 2H, q, J16, 17 s 6 Hz., 4.08 2H, q, J19, 20 s 8 Hz., 3.49 3H, s., 1.37 3H, t, J16, 17 s 8 Hz., 1.05 3H, t, J19, 20 s 8 Hz.. 13 C NMR CD 2 Cl 2 , 306 K, 50 MHz.: d 167.61, 166.88 1C, C5O., 155.08, 139.60, 137.04, 136.88, 136.34, 134.54, 132.55, 132.20, 131.38, 130.89, 123.21, 122.65, 62.61, 62.40, 14.68, 14.21. The polycondensation regimen is a general procedure described for the polymerisation of 8a to poly[(3X ,4Xdimethoxycarbonyl - 2X - hydroxy - 1,1X :5X ,1Y-terphenyl- 4,4Y ylene)] (10a). Ni COD . 0.67 g, 2.3 mmol., 1,5cyclooctadiene 0.21 g, 1.92 mmol. and 2,2X-bipyridyl 0.36 g, 2.3 mmol. were dissolved in dry DMF 2 ml. in a Schlenck tube under argon atmosphere. A solution of 1,5-bis 4-brom ophenyl . -2-hydroxy-3,4-dim ethoxy carbonylbenzene 1 g, 1.92 mmol. in dry DMF 2 ml. was added at room temperature. The resulting mixture was

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stirred at 608C for 16 h to a yellowishrgreen solution, which was precipitated with acidic-methanol HCl 10% vrv.. The precipitate was filtered off, washed with acidicmethanol HCl 10% vrv., ethanol, a hot aqueous solution of ethylenediaminetetraacetic acid EDTA. pH 3.8, a hot aqueous solution of EDTA pH 9, then distilled water, and dried under vacuum to give a yellowish solid 10a. 0.39 g, 57%.. Anal. calcd. for wC 22 H 16 O5 x required: C s 73.33%, H s 4.44%, Found: C s 64.16%, H s 4.20%, Br s 10.64%. IR-KBr.: n s 3456, 3444, 3440, 3433, 3430, 3413, 3406, 3040, 2960, 2856, 1737, 1675, 1604, 1435, 1349, 1237, 1203, 1178, 1130, 1010, 1006, 827 cmy1 . Optical absorption: lmax s 286 nm s 5833 My1 cmy 1 .. 1 H NMR CDCl 2 CDCl 2 , 306 K, 200 MHz.: d 11.40 1H, bs, D 2 O exchanged, OH., 7.59, 7.45, 7.20, 3.85, 3.61. 13 C NMR CDCl 2 CDCl 2 , 306 K, 50 MHz.: d 149.33 1C, C5O., 148.30 1C, C5O., 148.22, 135.83, 132.23, 131.54, 130.32, 129.89, 127.80, 110.20, 54.20, 53.17. Poly [( 3 X ,4 X -diethoxycarbonyl-2 X -hydroxy-1,1X :5 X ,1Y terphenyl-4,4Y-ylene)] (10b). 91 mg, 58%.. Anal. calcd. for wC 24 H 20 O5 x required: C s 74.23%, H s 5.16%, Found: C s 70.13%, H s 4.89%,Br s 3.50%. IR-KBr.: n s 3448, 3040, 2979, 2927, 2856, 1727, 1670, 1445, 1397, 1373, 1337, 1299, 1234, 1193, 1132, 1113, 1026, 1010, 824 cmy1 . Optical absorption: lmax s 292 nm s 6473 My1 cmy1 ., 356 nm s 5833 My1 cmy 1 .. Excitation: lmax s 269 nm. Emission: lmax s 463 nm. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 11.62 bs, D 2 O exchanged., 7.69, 7.54, 7.48, 7.26, 6.78, 4.42, 4.10, 1.56, 1.39, 1.08. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 169.98 1C, C5O., 168.54 1C, C5O., 158.62, 153.92, 145.75, 143.35, 140.20, 137.64, 136.00, 134.01, 133.28, 131.94, 130.01, 129.00, 127.02, 125.38, 124.02, 122.00, 112.60, 110.00, 62.82, 62.01, 14.01. Poly [(3X ,4 X -dipentoxycarbonyl-2 X -hydroxy-1,1X :5 X ,1Y terphenyl-4,4Y-ylene)] (10c). 260 mg, 68%.. Anal. calcd. for wC 30 H 32 O5 x required: C s 72.75%, H s 6.47%, Found: C s 73.76%, H s 6.77%,Br s 0.83%. IR-KBr.: n s 3406, 3032, 2979, 2944, 2864, 1723, 1683, 1679, 1674, 1669, 1652, 1644, 1641, 1635, 1621, 1611, 1495, 1395, 1369, 1335, 1311, 1301, 1255, 1234, 1192, 1134, 1113, 1096, 1026, 1015, 825 cmy1 . Optical absorption: l max s 287 nm s 7244 My1 cmy 1 ., 357 nm s 7559 My1 cmy 1 .. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 11.63 1H, bs, D 2 O exchanged., 7.54, 4.35, 4.01, 2.36, 1.73, 1.38, 1.12, 0.81, 0.29. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 169.01, 168.60 2C, C5O., 157.94, 140.01, 139.00, 137.67, 135.85, 134.02, 110.01, 67.20, 65.98, 27.99, 22.85, 14.02. Poly [( 3 X ,4 X -diethoxycarbonyl-2 X -methoxy-1,1X :5 X ,1Y terphenyl-4,4Y-ylene)] (10d). 260 mg, 96%.. Anal. calcd.

for wC 25 H 22 O5 x required: C s 73.71%, H s 5.41%, Found: C s 73.67%, H s 5.62%,Br s 0.93%. IR-KBr.: n s 3040, 2984, 2979, 2944, 1738, 1463, 1441, 1383, 1367, 1339, 1280, 1233, 1202, 1174, 1127, 1096, 1068, 1037, 1006, 827 cmy1 . Optical absorption: l max s 301 nm s 12 563 My1 cmy 1 .. Excitation: l max s 302 nm. Emission: lmax s 411 nm. 1 H NMR CDCl 3 , 306 K, 200 MHz.: d 7.74, 7.55, 7.46, 7.26, 4.44, 4.13, 3.58, 1.22, 1.01. 13 C NMR CDCl 3 , 306 K, 50 MHz.: d 167.90 1C, C5O., 166.89 1C, C5O., 154.67, 142.00, 140.01, 139.96, 137.38, 136.02, 134.03, 131.95, 130.01, 129.88, 127.96, 127.62, 62.67, 62.35, 14.28, 13.97.

Acknowledgements This work was sponsored by the Max Planck Gesellschaft Germany., and we extend our gratitude for their generosity. We would like to thank Herr Zimmer for the fluorescence measurements, and the staff of the GPC laboratory for providing molecular weight measurements.

References
w1x P. Kovacic, M.B. Jones, Chem. Rev. 87 1987. 357. w2x A.-D. Schluter, in: T.A. Skotheim, R.L. Elsenbaumer, J.R. Reynolds Eds.., Handbook of Conducting Polymers, 2nd edn., Marcel Dekker, New York, 1998, Chap. 8, p. 209. w3x T. Yamamoto, Y. Hagashi, A. Yamamoto, Bull. Chem. Soc. Jpn. 51 1978. 2091. w4x M. Rehahn, A.-D. Schluter, G. Wegner, W.J. Feast, Polymer 30 1989. 1054. w5x M. Rehahn, A.-D. Schluter, G. Wegner, W.J. Feast, Polymer 30 1989. 1060. w6x M. Rehahn, A.-D. Schluter, G. Wegner, Makromol. Chem. 191 1990. 1991. w7x U. Scherf, in: T.A. Skotheim, R.L. Elsenbaumer, J.R. Reynolds Eds.., Handbook of Conducting Polymers, 2nd edn., Marcel Dekker, New York, 1998, Chap. 14, p. 363. w8x T.I. Wallow, B.M. Novak, J. Am. Chem. Soc. 113 1991. 7411. w9x J.L. Musfeldt, J.R. Reynolds, D.B. Tanner, J.P. Ruiz, J. Wang, M. Pomerantz, J. Polym. Sci., Part B 32 1994. 2394. w10x J.L. Reddinger, J.R. Reynolds, Macromolecules 30 1997. 479. w11x T. Yamamoto, A. Morita, Y. Miyazaki, T. Maruyama, H. Wakayama, Z.-H. Zhou, Y. Nakamura, T. Kanbara, S. Sasaki, K. Kubota, Macromolecules 25 1992. 1214. w12x A.W. McCulloch, B. Stanovnik, D.G. Smith, A.G. McInnes, Can. J. Chem. 47 1969. 4319. w13x P. Vogel, B. Willhalm, H. Prinzbach, Helv. Chim. Acta 52 3. 1969. 584. w14x R.E. Lutz, C.E. McGinn, J. Am. Chem. Soc. 64 1942. 2585. w15x F. Barba, M.D. Velasco, A. Guirado, Synthesis 593 1984. .