Chem. Mater.

2006, 18, 1007-1015 1007

Effects of Methyl Substitution of

Poly(9-alkyl-9H-carbazole-2,7-diyl)s at the 3,6-Positions on Their
Physical Properties
Ahmed Iraqi,* David F. Pickup, and Hunan Yi
Department of Chemistry, UniVersity of Sheffield, Sheffield S3 7HF, U.K.
ReceiVed June 16, 2005. ReVised Manuscript ReceiVed NoVember 23, 2005

The preparation and characterization of poly(3,6-dimethyl-9-alkyl-9H-carbazole-2,7-diyl)s P1 and poly-

(3,6-dimethyl-9-alkyl-9H-carbazole-alt-9-alkyl-9H-carbazole-2,7 -diyl)s alternating copolymers P2 are
presented. The polymers were prepared via Suzuki cross-coupling reactions, and two different alkyl
substituents were used for both classes of polymers to investigate the effects of their different steric
bulks on the properties of the resulting materials. Both classes of materials provided wide-band-gap
polymers that emit in the blue part of the electromagnetic spectrum. Cyclic voltammetry studies on the
two classes of polymers indicate greater electrolytic stability of these new polymers as compared to
poly(9-alkyl-9H-carbazole-2,7-diyl)s as a result of a full or partial methyl functionalization of the 3,6-
positions on carbazole repeat units on the polymer chains. The new polymers are also thermally stable
up to 350 °C.

Introduction structural makeup and 3,6-linkage between consecutive

Currently, there is a considerable drive to develop highly carbazole repeat units, electronic conjugation in poly(9-alkyl-
fluorescent blue-light-emitting polymers. Such polymers not 9H-carbazole-3,6-diyl)s is limited to about two carbazole
only are required for efficient emission in the blue part of units; in addition, their quantum yields of fluorescence are
the electromagnetic spectrum, but could also serve as energy- fairly low.
transfer donors when used in conjunction with added lower- Polyfluorenes and poly(p-phenylene)s have attracted much
band-gap fluorophores.1 They could also be used as hosts interest in this area, and great advances have been achieved
for phosphorescent dyes in an effort to enable the use of with these materials. Recently, much effort has been directed
both singlet and triplet excitons in the radiative decay toward developing alternative polymers to these two classes
process.2 of materials, and special interest has focused on 2,7-linked
Carbazole-based polymers such as poly(vinylcarbazole) carbazole polymers.6 We have recently shown that poly(9-
(PVK) are used extensively in this area of research, chiefly alkyl-9H-carbazole-2,7-diyl)s7 offer many advantageous
as hole-transporting materials,3 but also as wide-band-gap properties such as high photoluminescence efficiencies and
hosts to lower-band-gap fluorophores.4 Poly(9-alkyl-9H- lower oxidation potentials than their polyfluorene analogues.
carbazole-3,6-diyl)s constitute another class of carbazole- These polymers also emit in the blue part of the electro-
based polymers that has also been targeted in the literature.5 magnetic spectrum; however, cyclic voltammetry studies on
This class of carbazole polymers differs from PVK, as these this class of polymers have revealed that they do oxidize
are main-chain carbazole polymers rather than linear poly- irreversibly under electrolytic conditions. We and others8
mers with pendant carbazole units. However, in view of their have explained this instability as arising from the high
reactivity of their unprotected 3,6-positions. A review on this
* Corresponding author. Tel.: +(44) 114 222 9566. Fax: +(44) 114 222 class of materials has recently been published. In this study,
9303. E-mail: a.iraqi@sheffield.ac.uk.
(1) Virgili, T.; Lidzey, D. G.; Bradley, D. D. C. AdV. Mater. 2000, 12, we present our results on the preparation of a range of 2,7-
58. linked 9-alkylcarbazole homopolymers and copolymers
(2) (a) O’Brien, D. F.; Giebeler, C.; Fletcher, R. B.; Cadby, A. J.; Palilis, where the 3,6-positions are fully and partly functionalized,
L. C.; Lidzey, D. G.; Lane, P. A.; Bradley, D. D. C.; Blau, W. Synth.
Met. 2001, 116, 379. (b) Cleave, V.; Yahioglu, G.; Le Barny, P.; respectively, with methyl substituents and examine their
Hwang, D.-H.; Holmes, A. B.; Friend, R. H.; Tessler, N. AdV. Mater. electrolytic stability and physical properties.
2001, 13, 44. (c) Guo, T.-F.; Chang, S.-C.; Yang, Y.; Kwong, R. C.;
Thompson, M. E. Org. Electron. 2000, 1, 15.
(3) Hong, H.; Sfez, R.; Yitzchaik, S.; Davidov, D. Synth. Met. 1999, 102, Experimental Section
1217.
(4) (a) Ohmori, Y.; Kajii, H.; Sawatani, T.; Ueta, H.; Yoshino, K. Thin
Solid Films 2001, 393, 407. (b) Liang, C.; Li, W.; Hong, Z.; Liu, X.; Materials. 2,7-Dibromo-9H-carbazole was obtained according
Peng, J.; Liu, L.; Lu, Z.; Xie, M.; Liu, Z.; Yu, J.; Zhao, D. Synth. to literature procedures.9 The sodium hydroxide was quickly ground
Met. 1997, 91, 151. (c) Lee, C.-L.; Lee, K. B.; Kim, J.-J. Mater. Sci.
Eng. B 2001, 85, 228. (d) Lamansky, S.; Kwong, R. C.; Nugent, M.;
Djurovich, P. I.; Thompson, M. E. Org. Electron. 2001, 2, 53. (6) Sigwalt, P.; Wegner, G.; Morin, J-F.; Leclerc, M.; Ades, D.; Siove,
(5) (a) Iraqi, A.; Wataru, I. J. Polym. Sci. A: Polym. Chem. 2004, 42, A. Macromol. Rapid Commun. 2005, 26, 761.
6041. (b) Zhang, Z.-B.; Fujiki, M.; Tang, H.-Z.; Motonaga, M.; (7) Iraqi, A.; Wataru, I. Chem. Mater. 2004, 16, 442.
Torimitsu, K. Macromolecules 2002, 35, 1988. (c) Faid, K.; Siove, (8) Zotti, G.; Schiavon, G.; Zecchin, S.; Morin, J.-F.; Leclerc, M.
A.; Ades, D.; Chevrot, C. Synth. Met. 1993, 55-57, 1656. Macromolecules 2002, 35, 2122.

10.1021/cm051305l CCC: $33.50 © 2006 American Chemical Society

Published on Web 01/28/2006
1008 Chem. Mater., Vol. 18, No. 4, 2006 Iraqi et al.

just before use when employed in the alkylation reactions of 2,7- ments were prepared by dip coating quartz plates into 0.1 mg cm-3
dibromo-9H-carbazole or 2,7-dibromo-3,6-dimethyl-9H-carbazole. polymer solutions in dichloromethane (HPLC grade), and the
Tetrahydrofuran (THF) was distilled over sodium benzophenone measurements were carried out at ambient temperature in air.
under inert nitrogen atmosphere. Toluene was dried and distilled The absorbances of the sample solutions at the excitation
over sodium under an inert argon atmosphere. Acetonitrile (HPLC wavelengths used were kept below 0.05 to obtain inner-filter-effect-
grade) was dried and distilled over phosphorus pentoxide under an free photoluminescence spectra. All photoluminescence spectra were
inert argon atmosphere and was then stored over molecular sieves corrected. The correction factors were obtained by excitation spectra
3A. 2,5-Dibromo-4-nitrotoluene was prepared according to literature measurements of the quantum counter (rhodamine B standard
procedures,10 as were 2,7-dibromo-9H-carbazole9 and 2,7-dibromo- solution) for the excitation side and by a synchronous wavelength
9-(2-hexyldecyl)-9H-carbazole (6a).7 scan using a light diffuser for the emission side. The light diffuser
Measurements. NMR spectra were recorded on Bruker 250 (part no. 650-1576) was provided with the spectrophotometer as
MHz, AMX400 400 MHz, or DRX500 500 MHz NMR spectrom- an accessory. The correction factors obtained were stored in the
eters at 22 °C in chloroform-d1 or acetone-d6 solution with TMS memory of the spectrophotometer. As a result, the spectrophotom-
as the internal standard. IR absorption spectra were recorded on eter automatically gave corrected excitation and emission spectra
the Nicolet model 205 FT-IR spectrometer. Liquid samples were when measurements were carried out.
analyzed neat using the NaCl-plate method, and solid samples were Harmine and quinine sulfate dihydrate in sulfuric acid (0.05 and
analyzed using the diamond ATR attachment for solid samples. 0.5 mol dm-3, respectively) were employed as fluorescence
Melting points were obtained using a Gallenkamp melting point standards. The quantum yields in dilute solutions were obtained
apparatus. GC-MS spectra were recorded on a Perkin-Elmer by comparison with a fluorescence standard of a known quantum
Turbomass mass spectrometer equipped with a Perkin-Elmer PE- yield using the equation
5MS capillary column. Mass spectra were obtained by the electron
Φx ) Φs(Ss/As)-1(Sx/Ax)(nx2/ns2)
impact method (EI) or the chemical ionization method (CI). GPC
curves were recorded on equipment consisting of a Waters Model where the subscripts s and x refer to the standard and the unknown
515 HPLC pump, a Gilson model 234 autoinjector, a Millipore sample solutions, respectively; Φ is the quantum yield; A is the
Waters Lambda-Max model 481 LC spectrometer, an Erma ERC- absorbance at the excitation wavelength used; S is the integral
7512 refractive index (RI) detector, a PLgel 5-m 500A column, intensity of the corrected photoluminescence spectra; and n is the
and a PLgel 10-m MIXED-B column using THF as the eluent at a refractive index of the solvent. The fluorescence standard solution
rate of 1 cm3 min-1. Polymer solutions in THF (2.5 mg cm-3) were and the unknown sample solution were excited at the same
used as samples for GPC analysis. The GPC curves were obtained wavelength. Quinine sulfate dihydrate solution in 0.5 mol dm-3
by the RI detection method, calibrated with a series of narrow sulfuric acid (Φs ) 0.546) was employed as the fluorescence
polystyrene standards (Polymer Laboratories). Elemental analyses standard solution. With regard to the refractive indexes of the
were carried out with a Perkin-Elmer 2400 CHN elemental analyzer solvents, values of 1.339, 1.334, and 1.424 were employed for 0.5
for CHN analysis and by the Schöniger oxygen flask combustion mol dm-3 sulfuric acid, 0.05 mol dm-3 sulfuric acid, and dichlo-
method for anion analysis. UV-visible absorption spectra were romethane, respectively. S/A values for each sample in solution
measured with a Hitachi U-2010 double-beam UV-visible spec- could simply be obtained by dividing the integral intensities of the
trophotometer. The absorbance of monomers and polymers was spectra by the absorbances at the excitation wavelengths employed
measured in a solution of dichloromethane (HPLC grade) at ambient using a sample solution of a certain concentration. To minimize
temperature using rectangular quartz cuvettes (light path length ) experimental error, the final S/A values used in the calculations
10 mm) purchased from Sigma-Aldrich. Samples of pristine for each sample were obtained from plots of the integral intensities
polymer thin films for UV-visible absorption spectra measurements of the spectra vs the absorbances at the excitation wavelengths
were prepared by dip coating quartz plates into 1 mg cm-3 polymer employed using sample solutions of various concentrations. The
solutions in dichloromethane (HPLC grade), and the measurements reliability of our measurements was confirmed upon measurement
were carried out at ambient temperature. Photoluminescence spectra of the quantum yield of harmine using quinine sulfate dihydrate as
were obtained using a Hitachi F-4500 fluorescence spectropho- the standard. The experimental value obtained was identical to that
tometer equipped with a Hamamatsu Photonics R928F photomul- reported in the literature (Φs ) 0.45).11
tiplier tube (PMT). PL solution measurements were carried out using TGA curves were obtained on a Perkin-Elmer Pyris 1 thermo-
a quartz fluorescence cuvette (light path length ) 10 mm) purchased gravimetric analyzer at a scan rate of 20 °C min-1 under an inert
from Sigma-Aldrich. Photoluminescence spectra measurements of nitrogen atmosphere. Platinum pans were used as sample pans. The
harmine and quinine sulfate dihydrate solutions were carried out weights of the samples were ca. 5 mg. Cyclic voltammograms were
in 0.05 and 0.5 mol dm-3 sulfuric acid, respectively, at 25 °C in recorded with equipment consisting of a Princeton Applied Research
air, as both harmine and quinine sulfate dihydrate exhibit no oxygen model 263A potentiostat/galvanostat. Measurements were carried
quenching effect. out under argon at 25 ( 2 °C. Tetrabutylammonium perchlorate
Photoluminescence spectra measurements of the polymer solu- (TBAClO4) solution in acetonitrile (0.1 mol dm-3, 10 cm3) was
tions were carried out in dichloromethane (HPLC grade) at 25 °C. used as the electrolyte solution. A three-electrode system was used.
The oxygen quenching effects of polymers P1 and P2 were The three electrodes consisted of a Ag/Ag+ reference electrode
examined by comparing the photoluminescence spectra of their (silver wire in 0.01 mol dm-3 silver nitrate solution in the electrolyte
solutions in air with those under an argon atmosphere. Because solution), a platinum working electrode (2-mm-diameter smooth
the solutions exhibited no oxygen quenching effect, photolumines- platinum disk, area ) 3.14 × 10-2 cm2), and a platinum counter
cence spectra measurements of their solutions were carried out in electrode (platinum wire). Polymer thin films were formed by drop-
air. Samples of pristine polymer thin films for PL spectra measure- casting 1.0 mm3 of polymer solution in dichloromethane (HPLC
grade) (1 mg cm-3) onto the working electrode and then drying in
air.
(9) Yamato, T.; Hideshima, C.; Suehiro, K.; Tashiro, M.; Prakash, G. K.
S.; Olah, G. A. J. Org. Chem. 1991, 56, 6248.
(10) Choy, N.; Russell, K. C.; Alvarez, J. C.; Fider, A. Tetrahedron Lett. (11) Pardo, A.; Reyman, D.; Poyato, J. M. L.; Medina, F. J. Lumin. 1992,
2000, 41, 1515. 51, 269.
Substitution of Poly(9-alkyl-9H-carbazole-2,7-diyl)s Chem. Mater., Vol. 18, No. 4, 2006 1009

Ferrocene was employed as the reference redox system according g, 72.0% yield). mp: 242.2-243.4 °C. The product gave a single
to IUPAC’s recommendation12 Polymer thin films were formed by peak on GC (retention time ) 11.34 min). IR (solid state): 3416,
drop-casting 1.0 mm3 of polymer solution in dichloromethane 2921, 2360, 1707, 1601, 1479, 1450, 1377, 1324, 1303, 1276, 1241,
(analytical reagent) (1 mg cm-3) onto the working electrode and 1210, 1053, 1038, 995, 972, 903, 874, 856, 809, 777, 724, 669,
then drying in air. 620, 598, 579, 570 cm-1. MS (EI) (m/z): 351, 353, 355 (M•+). 1H
Preparation of the Monomers. All reactions were carried out NMR (acetone-d6) δH (ppm): 2.50 (6H, s), 7.71 (2H, s), 8.02 (2H,
under inert nitrogen atmosphere. s), 10.46 (1H, s). 13C NMR (acetone-d6) δC (ppm): 23.0 (2C), 115.3
4,4′-Dibromo-5,5′-dimethyl-2,2′-dinitrobiphenyl (1). A mixture (2C), 122.4 (2C), 122.7 (2C), 123.1 (2C), 128.4 (2C), 140.7 (2C).
of 2,5-dibromo-4-nitrotoluene (25.70 g, 87.12 mmol) and copper Anal. Calcd for C14H11NBr2: C, 47.63; H, 3.14; N, 3.97; Br, 45.26.
powder (-150 mesh) (13.29 g, 209.08 mmol) in DMF (230 cm3) Found: C, 47.93; H, 3.30; N, 3.98; Br, 44.91.
was heated at 120 °C with stirring for 2 h. The reaction mixture 2,7-Dibromo-3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole (4a). A
was cooled to ambient temperature, and then toluene (350 cm3) mixture of 2,7-dibromo-3,6-dimethyl-9H-carbazole (3) (7.40 g,
was added. Unreacted copper powder and insoluble materials were 20.96 mmol), 7-bromomethylpentadecane (9.72 g, 31.83 mmol),
filtered off. The filtrate was washed with a saturated NaCl solution tetrabutylammonium hydrogensulfate (0.30 g, 0.88 mmol), and
(350 cm3 × 6) and dried over MgSO4, and then the solvent was NaOH (1.27 g, 31.75 mmol) in acetone (HPLC grade) (60 cm3)
removed in vacuo. The obtained residue was further dried in vacuo was refluxed for 16 h. After the reaction was completed, the acetone
to give 4,4′-dibromo-5,5′-dimethyl-2,2′-dinitrobiphenyl (1) as a was removed in vacuo, and the residue was extracted with toluene
yellow powder (16.01 g, 85.4% yield). mp: 246.0-247.9 °C (lit.13 (500 cm3). The toluene solution was washed with a saturated NaCl
228-230 °C). The product gave a single peak on GC (retention aqueous solution (350 cm3 × 3), dried over MgSO4, and evaporated
time ) 11.04 min). IR (solid state): 3106, 2961, 1596, 1562, 1513, to dryness in vacuo. The residue was purified by column chroma-
1434, 1382, 1338, 1283, 1260, 1117, 1095, 1057, 1034, 1012, 913, tography on silica gel 60 with hexane as the eluent to give 2,7-
894, 881, 840, 798, 761, 738, 699, 684, 658, 630, 620, 569, 545 dibromo-3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole (4a) as an oil
cm-1. 1H NMR (CDCl3) δH (ppm): 2.49 (6H, s), 7.11 (2H, s), 8.41 that turns to a white powder over time (11.72 g, 96.8% yield). mp:
(2H, s). 13C NMR (CDCl3), δC (ppm): 23.0 (2C), 124.8 (2C), 128.8 58.5-59.3 °C. The product gave a single peak on GC (retention
(2C), 132.3 (2C), 132.5 (2C), 145.0 (2C), 145.1 (2C). Anal. Calcd time ) 16.83 min). IR (solid state): 2935, 2918, 2852, 1601, 1556,
for C14H10N2O2Br2: C, 39.10; H, 2.34; N, 6.51; Br, 37.16. Found: 1478, 1466,1450, 1378, 1342, 1300, 1290, 1245, 1235, 1182, 1158,
C, 39.20; H, 2.79; N, 5.60; Br, 36.67. 1040, 996, 946, 922, 869, 844, 803, 781, 754, 722, 696, 672, 652,
4,4′-Dibromo-5,5′-dimethylbiphenyl-2,2′-diamine (2). To a mix- 627, 602, 576, 566, 544, 525, 517 cm-1. MS (EI) (m/z): 575, 577,
ture of 4,4′-dibromo-5,5′-dimethyl-2,2′-dinitrobiphenyl (1) (15.60 579 (M•+). 1H NMR (CDCl3) δH (ppm): 0.78-0.91 (6H, m), 1.14-
g, 36.27 mmol), ethanol (HPLC grade) (200 cm3), and 37 wt % 1.40 (24H, m), 2.04 (1H, septet, J ) 6 Hz), 2.54 (6H, s), 3.92 (2H,
hydrochloric acid (80 cm3) was added tin powder (-325 mesh) d, J ) 8 Hz), 7.48 (2H, s), 7.81 (2H, s). 13C NMR (CDCl3) δC
(17.22 g, 145.08 mmol). The reaction mixture was then refluxed (ppm): 14.10 (1C), 14.13 (1C), 22.67 (1C), 22.70 (1C), 23.01 (2C),
for 1.5 h, and an additional portion of tin powder (-325 mesh) 26.38 (1C), 26.41 (1C), 29.08 (1C), 29.29 (1C), 29.52 (1C), 29.61
(17.22 g, 145.08 mmol) was added. The reaction mixture was then (1C), 29.92 (1C), 31.65 (1C), 31.81 (1C), 31.89 (1C), 37.54 (1C),
refluxed for an additional period of 1.5 h. The reaction mixture 47.81 (1C), 112.62 (2C), 121.33 (2C), 121.59 (2C), 122.35 (2C),
was cooled to ambient temperature, and the unreacted tin powder 127.74 (2C), 140.37 (2C). Anal. Calcd for C30H43NBr2: C, 62.40;
was filtered off. The filtrate was poured onto a mixture of ice and H, 7.51; N, 2.43; Br, 27.67. Found: C, 62.69; H, 7.74; N, 2.35;
10 wt % NaOH aqueous solution (600 cm3) and then extracted with Br, 27.57.
diethyl ether (450 cm3 × 4). The diethyl ether layer was then
2,7-Dibromo-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole (4b).
washed with distilled water (300 cm3 × 3) and dried over MgSO4,
2,7-Dibromo-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole (4b) was
and then the solvent was removed in vacuo. The obtained residue
prepared according to the method used for 2,7-dibromo-3,6-
was further dried in vacuo to give 4,4′-dibromo-5,5′-dimethylbi-
dimethyl-9-(2-hexyldecyl)-9H-carbazole (4a), except that 2.50 g
phenyl-2,2′-diamine (2) as a pale yellow powder (11.26 g, 84%
(7.08 mmol) of 2,7-dibromo-3,6-dimethyl-9H-carbazole (3), 2.65
yield). The product gave a single peak on GC (retention time )
g (10.63 mmol) of 5-bromomethylundecane, 0.20 g (0.59 mmol)
12.86 min). mp: 122.1-123.9 °C. IR (solid state): 3402, 3294,
of tetrabutylammonium hydrogensulfate, and 0.70 g (17.50 mmol)
3092, 3015, 2960, 2869, 2017, 1967, 1918, 1848, 1789, 1715, 1615,
of NaOH were used in 50 cm3 of acetone (HPLC grade).
1584, 1525, 1474, 1438, 1349, 1324, 1291, 1268, 1194, 1135, 1102,
2,7-Dibromo-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole (4b) was
1074, 1002, 976, 925, 904, 880, 862, 823, 779, 718, 665, 652, 611,
isolated as a colorless oil (1.70 g, 46.0% yield). The product gave
594, 563, 534, 510 cm-1. MS (EI) (m/z): 368, 370, 372 (M•+). 1H
a single peak on GC (retention time ) 14.76 min). IR (solid state):
NMR (CDCl3) δH (ppm): 2.22 (6H, s), 3.34 (4H, s), 6.85 (2H, s),
2939, 2926, 2856, 1603, 1560, 1477, 1459, 1379, 1343, 1301, 1285,
6.91 (2H, s). 13C NMR (CDCl3) δC (ppm): 21.68 (2C), 118.88
1240, 1182, 1041, 997, 948, 931, 866, 836, 780, 725, 699, 672,
(2C), 119.04 (2C), 123.12 (2C), 127.70 (2C), 132.64 (2C), 142.98
603, 568, 508, 495 cm-1. MS (EI) (m/z): 519, 521, 523 (M•+). 1H
(2C). Anal. Calcd for C14H14N2Br2: C, 45.44; H, 3.81; N, 7.57;
NMR (CDCl3) δH (ppm): 0.79-0.92 (6H, m), 1.11-1.41 (16H,
Br, 43.18. Found: C, 45.39; H, 3.84; N, 6.99; Br, 46.47.
m), 2.04 (1H, septet), 2.54 (6H, s), 3.94 (2H, d, J ) 7.5 Hz), 7.48
2,7-Dibromo-3,6-dimethyl-9H-carbazole (3). A mixture of 4,4′-
(2H, s), 7.82 (2H, s). 13C NMR (CDCl3) δC (ppm): 14.00 (1C),
dibromo-5,5′-dimethylbiphenyl-2,2′-diamine (2) (11.10 g, 29.99
14.05 (1C), 22.61 (1C), 22.98 (2C), 26.33 (1C), 28.59 (1C), 29.58
mmol) and 4-dodecylbenzenesulfonic acid (19.60 g, 60.03 mmol)
(1C), 29.70 (1C), 31.37 (1C), 31.60 (1C), 31.77 (1C), 37.61 (1C),
in 5-tert-butyl-m-xylene (180 cm3) was refluxed for 24 h. The
47.87 (1C), 112.65 (2C), 121.35 (2C), 121.61 (2C), 122.37 (2C),
solution was evaporated to dryness upon distillation of the solvent
127.78 (2C), 140.43 (2C). Anal. Calcd for C26H35NBr2: C, 59.90;
in vacuo. The residue was purified by column chromatography on
H, 6.77; N, 2.69; Br, 30.65. Found: C, 60.09; H, 6.75; N, 2.46;
silica gel 60 with toluene/hexane (3/7, v/v) as the eluent to give
Br, 30.49.
2,7-dibromo-3,6-dimethyl-9H-carbazole (3) as a white powder (7.62
2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dimeth-
(12) Gritzner, G. Pure Appl. Chem. 1990, 62, 1839. yl-9-(2-hexyldecyl)-9H-carbazole (5a). t-Butyllithium (30.6 cm3,
(13) Le Fevre, R. J. W.; Turner, E. E. J. Chem. Soc. 1928, 963. 52.02 mmol, 1.7 M in pentane) was added dropwise to a solution
1010 Chem. Mater., Vol. 18, No. 4, 2006 Iraqi et al.

of 2,7-dibromo-3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole (4a) 2856, 1867, 1621, 1587, 1524, 1484, 1451, 1426, 1378, 1327, 1315,
(10.0 g, 17.32 mmol) in THF (500 cm3) at -78 °C. The reaction 1268, 1245, 1224, 1204, 1133, 1056, 1019, 999, 952, 928, 900,
mixture was stirred at -78 °C for 4 h. 2-Isopropoxy-4,4,5,5- 867, 839, 793, 741, 667, 594, 558 cm-1. MS (EI) (m/z): 491, 493,
tetramethyl-1,3,2-dioxaborolane (32.3 g, 17.36 mmol) was then 495 (M•+). 1H NMR (CDCl3) δH (ppm): 0.76-0.94 (6H, m), 1.08-
added dropwise to the solution at -78 °C, and the reaction mixture 1.44 (16H, m), 2.06 (1H, m), 4.01 (2H, d, J ) 7.5 Hz), 7.32 (2H,
was stirred at -78 °C for an additional 2 h. The reaction mixture dd, J ) 2 Hz, 8 Hz), 7.47 (2H, d, J ) 2 Hz), 7.85 (2H, d, J ) 2
was then allowed to warm to ambient temperature and stirred for Hz). 13C NMR (CDCl3) δC (ppm): 14.05 (1C), 14.13 (1C), 22.66
another 36 h. The reaction mixture was then poured onto water (1C), 23.04 (1C), 26.36 (1C), 28.61 (1C), 29.61 (1C), 31.38 (1C),
(600 cm3) and extracted with diethyl ether. The organic extracts 31.60 (1C), 31.80 (1C), 37.62 (1C), 47.81 (1C), 112.28 (2C), 119.64
were combined, washed with water (400 cm3 × 3), and dried over (2C), 121.20 (2C), 121.39 (2C), 122.49 (2C), 141.80 (2C). Anal.
MgSO4, and the solvent was removed in vacuo. The residue was Calcd for C24H31NBr2: C, 58.43; H, 6.33; N, 2.84; Br, 32.39.
purified by flash vacuum chromatography eluting first with hexane Found: C, 58.64; H, 6.26; N, 2.77; Br, 32.37.
to remove starting material and then with dichloromethane to obtain Preparation of the Polymers. All polymerizations were carried
the product. The dichloromethane solution was dried over MgSO4 out under an inert argon atmosphere. All polymers obtained were
and concentrated in vacuo to obtain 5a as a pale orange oil that stored in the dark.
turns to a pale orange solid over time (10.60 g, 91.1% yield). mp: Poly(3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole-2,7-diyl) (P1a).
67.6-68.4 °C. The product gave a single peak on GC (retention A solution of palladium(II) acetate (2.0 mg, 8.9 µmol) and
time ) 21.55 min). IR (solid state): 2943, 2924, 2852, 1551, 1458, triphenylphosphine (9.4 mg, 0.036 mmol) in toluene (3 cm3) was
1437, 1370, 1326, 1285, 1271, 1246, 1212, 1145, 1109, 1068, 1010, stirred at 50 °C for 15 min in a sealable tube. After this mixture
967, 858, 792, 738, 720, 701, 690, 676, 659, 594, 578 cm-1. MS had cooled to ambient temperature, a solution of 2,7-bis(4,4,5,5-
(EI) (m/z): 671, 672, 673 (M•+). 1H NMR (CDCl3) δH (ppm): tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dimethyl-9-(2-hexyldecyl)-
0.73-0.86 (6H, m), 1.09-1.30 (24H, m), 1.37 (24H, s), 2.12 (1H, 9H-carbazole (5a) (0.4541 g, 0.676 mmol) and 2,7-dibromo-3,6-
m), 2.62 (6H, s), 4.12 (2H, d, J ) 7 Hz), 7.74 (2H, s), 7.77 (2H, dimethyl-9-(2-hexyldecyl)-9H-carbazole (4a) (0.3807 g, 0.659
s). 13C NMR (CDCl3) δC (ppm): 14.11 (2C), 22.31 (1C), 22.61- mmol) in toluene (7 cm3) was added to the sealable tube and stirred
(2C), 22.66 (1C), 24.91 (8C), 26.42 (1C), 26.46 (1C), 29.30 (1C), at ambient temperature for 10 min. Then, 20 wt % tetraethylam-
29.58 (1C), 29.61 (1C), 29.69 (1C), 29.93 (1C), 31.74 (1C), 31.84 monium hydroxide (4 cm3, 5.43 mmol) was added, the glass tube
(1C), 31.90 (1C), 37.92 (1C), 47.16 (1C), 83.30 (4C), 116.56 (2C), was sealed, and the mixture was heated at 120 °C with stirring for
121.16 (4C), 124.42 (2C), 133.92 (2C), 139.40 (2C). Anal. Calcd 72 h. The mixture was allowed to cool to ambient temperature,
for C42H67B2NO4: C, 75.11; H, 10.06; N, 2.09. Found: C, 73.92; then bromobenzene (0.1 cm3, 0.950 mmol) was added, and the
H, 10.04; N, 1.97. mixture was stirred for an additional 1 h at 120 °C. The mixture
2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-dimeth- was again allowed to cool to ambient temperature, after which
yl-9-(2-butyloct yl)-9H-carbazole (5b). 2,7-Bis(4,4,5,5-tetramethyl- phenylboronic acid (0.12 g, 0.984 mmol) was added, and the
1,3,2-dioxaborolan-2-yl)-3,6-dimethyl-9-(2-butyloc tyl)-9H-carba- mixture was stirred for an additional 1 h at 120 °C. After cooling
zole (5b) was prepared according to the method used for 5a, except to ambient temperature, the mixture was poured onto methanol (500
that 4.0 cm3 (6.80 mmol, 1.7 M in pentane) of tert-butyllithium cm3). The precipitates were filtered off and dissolved in chloroform
was added dropwise to a solution of 1.17 g (2.24 mmol) of 2,7- (200 cm3). The insoluble materials in the chloroform solution were
dibromo-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole (4b) in 90 cm3 filtered off, and then the filtrate was concentrated in vacuo. The
of THF at -78 °C. After this solution had been stirred for 4 h, 4.2 concentrated chloroform solution (∼20 cm3) was poured onto
g (22.57 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-diox- methanol (500 cm3), and the precipitates were filtered off and dried
aborolane was then added dropwise at -78 °C. 5b was isolated as in vacuo to give poly(3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole-
a white solid (1.21 g, 87.6% yield). mp: 117.2-118.9 °C. The 2,7-diyl) (P1a) as a white powder (0.47 g, 84.2% yield). GPC: Mw
product gave a single peak on GC (retention time ) 18.47 min). ) 9200, Mn ) 4400, Mw/Mn ) 2.1.
IR (solid state): 2945, 2923, 2854, 1554, 1438, 1387, 1370, 1329, Polymer P1a was also made under similar conditions using
1287, 1273, 1245, 1214, 1142, 1112, 1070, 1009, 969, 859, 837, palladium(II) acetate and tri-p-tolylphosphine in a ratio of 1/3 and
791, 738, 720, 700, 676, 659, 594, 582 cm-1. MS (EI) (m/z): 615, was obtained as a white powder in 86.8% yield. GPC: Mw )
616, 617 (M•+). 1H NMR (CDCl3) δH (ppm): 0.74-0.90 (6H, m), 13 500, Mn ) 6500, Mw/Mn ) 2.1. IR (solid state): 2932, 2921,
1.10-1.29 (16H, m), 1.31 (24H, s), 2.07 (1H, m), 2.63 (6H, s), 2853, 1867, 1609, 1465, 1376, 1348, 1289, 1236, 1224, 992, 868,
4.12 (2H, d, J ) 7 Hz), 7.75 (2H, s), 7.78 (2H, s). 13C NMR (CDCl3) 846, 780, 722, 667, 618, 588, 567, 557, 523, 492 cm-1. 1H NMR
δC (ppm): 14.12 (1C), 14.21 (1C), 22.33 (2C), 22.64(1C), 23.00 (CDCl3) δH (ppm): 0.69-0.93 (6H, m), 1.01-1.49 (24H, m), 2.03-
(1C), 24.93 (8C), 26.46 (1C), 28.60 (1C), 29.63 (1C), 31.37 (1C), 2.22 (1H, m), 2.25 (6H, s), 4.00-4.26 (2H, m), 7.28 (2H, s), 8.04
31.74 (1C), 31.86 (1C), 37.89 (1C), 47.06 (1C), 83.34 (4C), 116.58 (2H, s). 13C NMR (CDCl3) δC (ppm): 14.03 (1C), 14.11 (1C), 20.18
(2C), 121.18 (4C), 124.45 (2C), 133.96 (2C), 139.44 (2C). Anal. (1C), 22.61 (1C), 22.64 (2C), 26.40 (2C), 29.27 (1C), 29.49 (1C),
Calcd for C38H59B2NO4: C, 74.15; H, 9.66; N, 2.28. Found: C, 29.66 (1C), 30.00 (1C), 30.09 (1C), 31.70 (1C), 31.88 (2C), 37.90
74.84; H, 9.98; N, 2.23. (1C), 47.97 (1C), 109.74 (2C), 120.69 (2C), 121.31 (2C), 126.44
2,7-Dibromo-9-(2-butyloctyl)-9H-carbazole (6b). 2,7-Dibromo- (2C), 139.82 (2C), 140.45 (2C). Anal. Calcd for (C30H43N)n: C,
9-(2-butyloctyl)-9H-carbazole (6b) was prepared according to the 86.27; H, 10.38; N, 3.35. Found: C, 86.27; H, 10.80; N, 3.30.
literature procedure for 2,7-dibromo-9-(2-hexyldecyl)-9H-carbazole Poly(3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole-2,7-diyl) (P1b).
(6a),7 except that 1.50 g (4.62 mmol) of 2,7-dibromo-9H-carbazole, Poly(3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole-2,7-diyl) (P1b)
1.73 g (6.94 mmol) of 2-butyl-1-bromooctane, 0.2 g (0.59 mmol) was prepared according to the method used for P1a, except that
of tetrabutylammonium hydrogensulfate, 0.28 g (7.00 mmol) of 9.4 mg (0.036 mmol) of triphenylphosphine, 0.3626 g (0.5891
NaOH, and 40 cm3 of acetone (HPLC grade) were used. 2,7- mmol) of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,6-
Dibromo-9-(2-butyloctyl)-9H-carbazole (6b) was obtained as a dimethyl-9-(2-butyloctyl)-9H-carbazole (5b), 0.2843 g (0.5453
colorless oil (2.20 g, 96.6% yield). The product gave a single peak mmol) of 2,7-dibromo-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole
on GC (retention time ) 13.63 min). IR (solid state): 2938, 2926, (4b), and 4 cm3 (5.43 mmol) of tetraethylammonium hydroxide
Substitution of Poly(9-alkyl-9H-carbazole-2,7-diyl)s Chem. Mater., Vol. 18, No. 4, 2006 1011

were used. Poly(3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole-2,7- Scheme 1a

diyl) (P1b) was obtained as a white powder (0.26 g, 63.4% yield).
GPC: Mw ) 25 100, Mn ) 12 100, Mw/Mn ) 2.1. IR (solid state):
2934, 2921, 2855, 2360, 1610, 1467, 1376, 1353, 1287, 1238, 1202,
1176, 1036, 991, 922, 868, 839, 780, 725, 701, 668, 636, 585, 546,
526, 516, 498 cm-1. 1H NMR (CDCl3) δH (ppm): 0.69-0.90 (6H,
m), 1.04-1.45 (16H, m), 1.99-2.23 (1H, m), 2.26 (6H, s), 3.97-
4.31 (2H, m), 7.27 (2H, s), 8.04 (2H, s). 13C NMR (CDCl3) δC
(ppm): 13.98 (1C), 14.02 (1C), 20.14 (1C), 22.60 (1C), 23.06 (2C),
26.43 (1C), 28.57 (1C), 29.67 (2C), 31.49 (1C), 31.70 (1C), 31.93
(1C), 37.91 (1C), 48.03 (1C), 109.76 (2C), 120.69 (2C), 121.79
(2C), 126.49 (2C), 139.85 (2C), 140.49 (2C). Anal. Calcd for
(C26H35N)n: C, 86.37; H, 9.76; N, 3.87. Found: C, 85.14; H, 9.56;
N, 3.65.
Poly(3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole-alt-9-(2-hexy-
ldecyl)-9H-carb azole-2,7-diyl) (P2a). Poly(3,6-dimethyl-9-(2-hexy-
ldecyl)-9H-carbazole-alt-9-(2-hexyldecyl)-9H-carb azole-2,7-diyl)
(P2a) was prepared according to the method used for P1a, except
that 0.6701 g (0.998 mmol) of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)-3,6-dimethyl-9-(2-hexyldecyl)-9H-carbazole (5a)
and 0.5348 g (0.973 mmol) of 2,7-dibromo-9-(2-hexyldecyl)-9H-
carbazole (6a) were used. Poly(3,6-dimethyl-9-(2-hexyldecyl)-9H-
carbazole-alt-9-(2-hexyldecyl)-9H-carbaz ole-2,7-diyl) (P2a) was
a Conditions: (i) Cu, DMF. (ii) (a) Sn, HCl, EtOH; (b) NaOH. (iii)
obtained as a white powder (0.64 g, 80.4% yield). GPC: Mw )
C12H25(C6H4)SO3H, 5-tert-butyl-m-xylene. (iv) RBr, NaOH, (n-C4H9)4N-
31 200, Mn ) 13 900, Mw/Mn ) 2.2. IR (solid state): 2931, 2922, (HSO4), acetone. (v) (a) t-BuLi; (b) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-
2853, 1602, 1560, 1454, 1374, 1323, 1285, 1239, 1209, 1136, 1068, dioxaborolane, THF. (vi) (a) [Pd], NEt4OH, toluene; (b) PhB(OH)2; (c) PhBr.
1031, 1001, 868, 852, 811, 782, 722, 694, 630, 589, 560, 548, 533,
499 cm-1. 1H NMR (CDCl3) δH (ppm): 0.66-0.94 (6H, m), 1.02-
1.52 (24H, m), 2.11-2.34 (1H, m), 2.54 (6H, s), 4.00-4.42 (2H, Results and Discussion
m), 7.34 (2H, s), 7.38 (2H, d, J ) 7 Hz), 7.49 (2H, s) 8.05 (2H, s), Synthesis and Characterization of the Polymers. The
8.22 (2H, d, J ) 7 Hz). 13C NMR (CDCl3) δC (ppm): 14.06 (2C), preparation of polymers P1 and P2 was initiated by the
14.10 (2C), 21.05 (2C), 22.64 (C), 26.41 (2C), 26.67 (2C), 29.30 synthesis of monomers 4 and 5 as depicted in Scheme 1.
(2C), 29.33 (C), 29.53 (2C), 29.57 (1C), 29.70 (2C), 29.75 (1C), Ullmann coupling of the known 2,5-dibromo-4-nitrotoluene10
30.06 (1C), 31.74 (2C), 31.79 (1C), 31.87 (2C), 31.90 (1C), 32.11 afforded 4,4′-dibromo-5,5′-dimethyl-2,2′-dinitrobiphenyl (1)
(2C), 37.87 (1C), 38.21 (1C), 47.84 (1C), 47.99 (1C), 110.10 (2C), in 85% yield. This was then followed by reduction of 1 in
110.35 (2C), 119.67 (2C), 120.88 (2C), 121.39 (4C), 121.75 (2C),
a second step to afford 4,4′-dibromo-5,5′-dimethylbiphenyl-
125.95 (2C), 140.3 (2C), 140.68 (2C), 140.79 (2C), 141.24 (2C).
Anal. Calcd for (C58H82N2)n: C, 86.29; H, 10.24; N, 3.47. Found:
2,2′-diamine (2) in 84% yield. Reaction of 4-dodecylben-
C, 86.15; H, 10.27; N, 3.38. zenesulfonic acid with 2 in refluxing 5-tert-butyl-m-xylene
afforded 2,7-dibromo-3,6-dimethyl-9H-carbazole (3) in 72%
Poly(3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole-alt-9-(2-butyloc-
yield. 9-Alkyl-2,7-dibromo-3,6-dimethyl-9H-carbazole de-
tyl)-9H-carbazole-2,7-diyl) (P2b). Poly(3,6-dimethyl-9-(2-butyloc-
tyl)-9H-carbazole-alt-9-(2-butyloctyl)-9H-carba zole-2,7-diyl) (P2b) rivatives (4) were prepared in quantitative yields, upon
was prepared according to the method used for P1a, except that alkylation of 3 in the presence of a phase-transfer catalyst
0.4374 g (0.711 mmol) of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-diox- following a modified literature procedure for the alkylation
aborolan-2-yl)-3,6-dimethyl-9-(2-butyloctyl)-9H-carbazole (5b) and of carbazoles.14 Two branched alkyl substituents of different
0.3418 g (0.693 mmol) of 2,7-dibromo-9-(2-butyloctyl)-9H-carba- steric requirements were used in this study to probe the
zole (6b) were used. Poly(3,6-dimethyl-9-(2-butyloctyl)-9H-car- effects of their steric bulk on the physical properties of the
bazole-alt-9-(2-butyloctyl)-9H-carbazol e-2,7-diyl) (P2b) was ob- new polymers. The 9-alkyl-3,6-dimethyl-2,7-bis-(4,4,5,5-
tained as a white powder (0.30 g, 61.5% yield). GPC: Mw ) 27 700, tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-car bazole deriva-
Mn ) 10 100, Mw/Mn ) 2.7. IR (solid state): 2935, 2923, 2853, tives (5) were also obtained in quantitative yields upon
1601, 1560, 1453, 1373, 1322, 1285, 1240, 1199, 1134, 1062, 1036, lithium-halogen exchange of derivatives 4 upon reaction
1001, 917, 851, 810, 781, 724, 691, 672, 623, 588, 566, 530, 520,
with tert-butyllithium at low temperature, followed by
503, 498 cm-1. 1H NMR (CDCl3) δH (ppm): 0.55-0.91 (12H, m),
0.95-1.46 (32H, m), 1.97-2.26 (2H, m), 2.45 (6H, s), 3.89-4.34
quenching with 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-di-
(4H, m), 7.27 (2H, s), 7.31 (2H, d, J ) 7 Hz), 7.42 (2H, s), 7.98 oxaborolane. Polymers P1 and P2 were prepared using a
(2H, s), 8.14 (2H, d, J ) 7 Hz). 13C NMR (CDCl3) δC (ppm): 13.59 Suzuki-type cross-coupling condensation polymerization
(2C), 13.99 (1C), 14.04 (1C), 21.03 (2C), 22.60 (1C), 22.63 (1C), reaction (Scheme 1). The polymerization reactions were
23.08 (2C), 26.41 (1C), 26.48 (1C), 26.66 (2C), 28.60 (1C), 28.69 carried out using palladium acetate and triphenylphosphine
(1C), 29.70 (1C), 29.75 (1C), 30.92 (1C), 31.73 (1C), 31.79 (1C), as precursor catalysts in a ratio of 1 to 4 for all polymers
32.10 (1C), 37.90 (1C), 38.19 (1C), 47.89 (1C), 48.05 (1C), 110.09 and tetra-n-butylammonium hydroxide as a base in toluene
(2C), 110.36 (2C), 119.67 (2C), 120.90 (2C), 121.32 (2C), 121.39 in sealable autoclaves at 120 °C.
(2C), 121.77 (2C), 125.99 (2C), 140.14 (2C), 140.72 (2C), 140.82
(2C), 141.26 (2C). Anal. Calcd for (C50H66N2)n: C, 86.40; H, 9.57; (14) Beginn, C.; Gražulevičius, J. V.; Strohriegl, P.; Simmerer, J.; Haarer,
N, 4.03. Found: C, 86.23; H, 9.58; N, 3.90. D. Macromol. Chem. Phys. 1994, 195, 2353.
1012 Chem. Mater., Vol. 18, No. 4, 2006 Iraqi et al.

Table 1. Molecular Weight Distributions of Polymers P1 and P2 8.22, 7.49, and 7.34 ppm, respectively, corresponding to the
polymer Mn Mw polydispersity DPa three chemical environments of hydrogens at the 4,5-, 1,8-,
P1a 4400 9200 2.1 11 and 3,6-positions, respectively, of the carbazole repeat units
P1ab 6500 13 500 2.1 16 with no methyl substituents. In addition, in the aromatic
P1b 12 100 25 100 2.1 33
P2a 13 900 31 200 2.2 34
region, there are two broad peaks centered around 8.05 and
P2b 10 100 27 700 2.7 29 7.38 ppm, corresponding to the two chemical environments
a Degree of polymerization. b Palladium acetate/tri-p-tolylphosphine (1/3 of hydrogens at the 1,8- and 4,5-positions, respectively, of
ratio) used as the catalyst. the carbazole repeat units with methyl substituents at the 3,6-
positions. In addition, broad peaks centered around 4.20 ppm,
Gel permeation chromatography results from these po- corresponding to hydrogens of the methylene groups directly
lymerization reactions are reported in Table 1. Under these attached to the 9-position of the carbazole rings, were
polymerization conditions, the degree of polymerization (DP) observed for polymers P2. Peaks corresponding to the
of polymer P1b is much higher than that of polymer P1a hydrogen atoms of the methyl substituents at the 3,6-positions
(33 vs 11). Preparation of homopolymer P1a under similar on alternate carbazole repeat units appear around 2.50 ppm.
conditions using palladium acetate and tri-p-tolylphosphine 13
C NMR studies on polymers P2 reveal, in the aromatic
as precursor catalysts in a ratio of 1 to 3 gave a polymer region, 12 peaks corresponding to the different chemical
with a slightly higher degree of polymerization (DP ) 16), environments of the two different carbazole repeat units.
which was still lower than that of polymer P1b. These results These NMR results indicate a homogeneous structure of the
indicate that sterically demanding substituents on the car- alternating copolymers P2 prepared in this study with
bazole ring have a negative effect on the polymerization exclusive 2,7-linkage of the carbazole repeat units on the
reaction in the preparation of homopolymers P1. These polymer chains.
effects are, however, not observed in the preparation of Solution and Solid-State Electronic Spectra. The extent
copolymers P2, as both copolymers P2a and P2b have of π-orbital overlap between neighboring repeat units on
similar degrees of polymerization (DP ≈ 30), regardless of polymers P1 and P2 can be directly assessed from their
the bulk of the alkyl chains (2-hexyldecyl or 2-butyloctyl). electronic spectra. Table 2lists the absorption maxima values,
These results suggest that the presence of methyl substituents for the different carbazole polymers both in solution and in
on alternate carbazole rings at the ortho positions of the the solid state (films). Polymers P1 display maximum
coupling sites do not affect the polymerization, even if bulky absorptions in solution (dichloromethane) at a λmax value of
alkyl substituents are attached to the carbazole ring, as 317 nm (Table 2). In addition, absorption shoulder peaks at
opposed to polymerization reactions where both coupling 346 and 360 nm are also clearly evident in these spectra
partners have methyl substituents, as is the case for polymers (Figure 1). These could be explained by the existence of
P1. segments of more extended electronic conjugation along the
NMR Spectroscopy. NMR studies were conducted in polymer chains, on the basis of the fact that the relative
chloroform on the resulting carbazole polymers. 1H NMR intensities of these shoulder peaks increase with increasing
studies on poly(3,6-dimethyl-9-alkyl-9H-carbazole-2,7-diyl)s molecular weights of the polymers. The electronic spectra
(P1) reveal, in the aromatic region, two broad peaks with of these polymers in the solid state display features similar
equal integral intensities, centered around 8.04 and 7.28 ppm, to those recorded in solution with very close absorption
corresponding to the two chemical environments of hydro- maxima values (λmax ) 318 nm), as well as shoulder peaks
gens at the 1,8- and 4,5-positions, respectively, of the at 343 and 360 nm for P1a and at 345 and 359 nm for P1b.
carbazole rings. In addition, broad multiplets centered around The presence of methyl substituents at the 3,6-positions on
4.13 ppm, corresponding to hydrogens of the methylene consecutive carbazole repeat units in these polymers clearly
groups directly attached to the 9-position of the carbazole reduces the planarity of the polymer backbones and leading
rings, were observed for polymers P1a and P1b. Peaks to high band gap materials with Eg ≈ 3.2 eV as determined
corresponding to the hydrogen atoms of methyl substituents from the onset position of their absorption bands.
at the 3,6-positions of the carbazole repeat units appear Polymers P2 display maximum absorptions in solution
around 2.26 ppm. (dichloromethane) at a λmax value of around 342 nm (Table
13C NMR studies on polymers P1 reveal six chemical
2). The electronic spectra of these polymers in the solid state
environments with signals at around 140.4, 139.8, 126.4, display a small red shift with a λmax value of 350 nm,
121.7, 120.7, and 109.7 ppm, corresponding to carbons at indicating slightly more electronic conjugation in the solid
the 8a,9a-, 3,6-, 2,7-, 4,5-, 4a,4b-, and 1,8-positions, respec- state (Figure 2). The band gap of polymers P2 as determined
tively, of the carbazole rings. These NMR results indicate a from the onset position of their absorption bands, Eg, is
homogeneous structure for the poly(3,6-dimethyl-9-alkyl- around 2.95 eV. It is clear from these data that the electronic
9H-carbazole-2,7-diyl)s (P1) prepared in this study with conjugation in polymers P2 is more extended than that in
exclusive 2,7-linkage of the carbazole repeat units on the polymers P1 as a result of the absence of methyl groups on
polymer chains. alternate carbazole repeat units in the former polymers.
1H NMR studies on alternating copolymers poly(3,6- Solution and Solid-State Fluorescence Spectra. Fluo-
dimethyl-9-alkyl-9H-carbazole-alt-9-alkyl-9H-carbazole-2,7- rescence studies on polymers P1 and P2 were performed
diyl)s (P2) reveal, in the aromatic region, a broad doublet, both in solution (dichloromethane) and in the solid state. The
a broad singlet, and another broad doublet, centered around results of these studies are reported in Table 2. Fluorescence
Substitution of Poly(9-alkyl-9H-carbazole-2,7-diyl)s Chem. Mater., Vol. 18, No. 4, 2006 1013

Table 2. UV-Vis and Fluorescence Data for Polymers P1 and P2

absorption, λmaxa (nm) emission, λmaxa (nm)
Stokes shift band gapc
polymer CH2Cl2 film CH2Cl2 film Φβ (CH2Cl2) (nm) (eV)
P1a 317 (346, 360) 318 (343, 360) 393 397 (453, 468, 495) 0.16 79 3.21
P1b 317 (346, 360) 318 (345, 359) 392 396 (441, 468, 496) 0.25 78 3.21
P2a 342 350 397 400 (450, 470, 495) 0.64 50 2.95
P2b 341 350 397 403 (450, 460, 495) 0.51 53 2.95
a Numbers in parentheses correspond to shoulder absorption and emission peaks. b Measured using quinine sulfate dihydrate as the standard. c Determined

from the onset position of the absorption band.

Figure 1. Normalized absorption spectra of P1a in dichloromethane (solid

line) and as a thin film (long dashed line) and normalized emission spectra
of P1a in dichloromethane (dash-dotted line) and as a thin film (dash-dot-
dotted line).

Figure 3. Comparison of normalized emission spectra of thin films of (a)

P1a (long dashed line) and P1b (solid line) and (b) P2a (long dashed line)
and P2b (solid line).

Figure 2. Normalized absorption spectra of P2a in dichloromethane (solid broader emission spectra and larger full width at half-
line) and as a thin film (long dashed line) and normalized emission spectra maximum (fwhm) values in the two respective classes for
of P2a in dichloromethane (dash-dotted line) and as a thin film (dash-dot-
dotted line). polymers with shorter alkyl chains (P1b and P2b) when
compared to those with longer alkyl chains (P1a and P2a).
spectra of polymers P1 in solution showed emission bands This could be explained as arising from a propensity for less
centered on λmax values between 392 and 393 nm. The aggregation in the polymers with bulkier alkyl chains;
fluorescence spectra of these polymers in the solid state however, further work involving lifetime measurements is
showed emission bands between 396 and 397 nm with required to confirm this assumption.
shoulder peaks between 441 and 496 nm (Figure 1). These The fluorescence quantum yields of the polymers in
polymers display large Stokes shifts (about 80 nm), which dichloromethane solution were also determined. These were
points to large structural differences between the ground and determined upon excitation of the polymers at their λmax
excited states in these materials, both in solution and in the values and by comparison with the solution emission of
solid state. Fluorescence spectra of polymers P2 in solution quinine sulfate dihydrate (Φfl ) 0.546) used as the standard.
showed emission bands centered on a λmax value of 397 nm. The fluorescence quantum yields of these polymers are listed
The fluorescence spectra of these polymers in the solid state in Table 2. Homopolymers P1 displayed quantum yields
showed emission bands between 400 and 403 nm with ranging from 0.16 to 0.25. These values are higher than those
shoulder peaks between 450 and 495 nm (Figure 2). These obtained in previous studies for poly(9-alkyl-9H-carbazole-
polymers display smaller Stokes shifts (∼50 nm) than 3,6-diyl)s,5a which were found to be between 0.04 and 0.06.
homopolymers P1, which points to smaller structural dif- Copolymers P2 were found to be highly fluorescent, with
ferences between the ground and excited states in these quantum yields Φ ranging from 0.51 to 0.64, indicating their
materials, both in solution and in the solid state, when great potential for application in light-emitting diodes.
compared to polymers P1. Electrochemical Studies. Investigations of the electro-
Comparison of the fluorescence spectra of thin films of chemical properties of polymers P1 and P2 were also
homopolymers P1 and copolymers P2 (Figure 3) indicates undertaken in this study. Cyclic voltammetry measurements
1014 Chem. Mater., Vol. 18, No. 4, 2006 Iraqi et al.

Figure 5. TGA results for P1b (solid line), P2b (long dashed line), P1a
(dash-dotted line), and P2a (dotted line).

V, as well as a less distinct second oxidation wave at Epa

potentials of around 0.95 V. A reduction wave at the potential
Epc ) 0.81 V is observed for both P2a and P2b. This class
of materials has methyl substituents at the 3,6-positions on
alternate carbazole repeat units, and although it is conceivable
that some side reactions involving the formation of new
species might be occurring as a result of the creation of new
linkages between the 3,6-positions of adjacent polymer chains
within the films from the carbazole repeat units with no
Figure 4. CV curves (second scan) of thin films of (a) P1b and (b) P2b
methyl substituents on the copolymer chains, it must be noted
on a platinum disk electrode (area 0.031 cm2) at a scan rate of 100 mV s-1 that the electroactivity of these polymers is preserved after
in acetonitrile/tetrabutylammonium perchlorate (0.1 mol dm-3). several cycles at a scan rate of 100 mV s-1 as opposed to
Table 3. Redox Potentials of P1 and P2 in 0.1 M TBAClO4/CH3CN the electroactivity of poly(9-alkyl-9H-carbazole-2,7-diyl)s,7
on Pt Working Electrode at 100 mV s-1 Using Ag/Ag+ Reference which is lost at the first few cycles under similar conditions.
Electrode
The ionization potentials (vs vacuum) of polymers P1 and
polymer Epa (V) Epc (V) IPa (eV) P2 were estimated from the onset of their oxidation in cyclic
P1a 0.93 0.87 5.5 voltammetry responses at 5.5 and 5.2 eV, respectively (on
P1b 0.93 0.83 5.5
P2a 0.70 0.81 5.2 the basis that ferrocene/ferrrocenium is 4.8 eV below the
0.95b vacuum level15). The lower ionization potential of polymers
P2b 0.77 0.81 5.2 P2 could originate from the fact that they have a higher
0.95b
electronic conjugation than polymers P1. It must also be
a Ionization potential (vs vacuum) determined from onset of oxidation.
b noted that the ionization potentials of polymers P1 and P2
Second oxidation peak not clearly defined.
are 0.3 to 0.6 eV lower, respectively, than those of poly-
on drop-cast polymer films were conducted in acetonitrile (9,9-dioctyl-fluorene-2,7-diyl).16 The ionization potentials of
with tetrabutylammonium perchlorate as the electrolyte. The polymers P1 and P2 are also lower than that of poly-
cyclic voltammograms of polymers P1b and P2b are shown (vinylcarbazole) reported as ranging from 5.85 to 6.0 eV.17
in Figure 4 as representative examples of the two classes of This could suggest an easier hole injection into films from
polymers. The redox potentials of the various polymers as indium tin oxide (ITO) electrodes in device applications such
well as their respective ionization potentials (vs vacuum) are as light-emitting diodes.
reported in Table 3.
Thermal Gravimetric Analysis. Thermal gravimetric
The redox behavior of polymers P1 indicates a reversible
analysis (TGA) studies were also conducted on polymers
redox wave with an oxidation wave at the potential Epa )
P1 and P2 and revealed a good stability of these materials
0.93 V and an associated reduction wave at potentials Epc
up to 350 °C. The subsequent degradation and weight loss
between 0.83 and 0.87 V. The oxidative reversibility of these
in these materials beyond ∼560 °C was proportional to the
polymers is to be contrasted with that of poly(9-alkyl-9H-
mass of their alkyl substituents, as shown in Figure 5. This
carbazole-2,7-diyl)s7 and indicates the stabilizing effect of
indicates a degradation path affecting the alkyl substituents
introducing methyl substituents at the 3,6-positions in this
in a first instance. The polymers did not show any further
new class of materials on the electrolytic stability of the
weight loss up to a temperature of 800 °C.
resulting materials. Indeed, the electrolytic instability of the
poly(9-alkyl-9H-carbazole-2,7-diyl)s was attributed to the
formation of new species as a result of the creation of new (15) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, R. F.; Bässler, H.;
Porsch, M.; Daub, J. AdV. Mater. 1995, 7, 551.
linkages between the 3,6-positions of adjacent polymer chains (16) Janietz, S.; Bradley, D. D. C.; Grell, M.; Giebeler, C.; Inbasekaran,
within the films.7,8 The redox behavior of polymers P2 differs M.; Woo, E. P. Appl. Phys. Lett. 1998, 73, 2453.
(17) (a) Eiji, I.; Takanori, Y.; Keiichi, M. Thin Solid Films 2001, 393,
from that of polymers P1. The cyclic voltammograms of P2 368. (b) Shirota, Y.; Matsumoto, Y.; Mikawa, H.; Seki, K.; Inokuchi,
show a first oxidation wave at Epa potentials of around 0.7 H. Chem. Phys. Lett. 1983, 97, 57.
Substitution of Poly(9-alkyl-9H-carbazole-2,7-diyl)s Chem. Mater., Vol. 18, No. 4, 2006 1015

Conclusion yields in solution (between 0.16 and 0.25), whereas copoly-

mers P2 displayed higher fluorescence quantum yields in
The development of preparation routes of two new classes
solution (between 0.51 and 0.64). The copolymers have
of 2,7-linked poly(9-alkyl-9H-carbazole-2,7-diyl)s with meth-
different electrochemical properties than the homopolymers.
yl substituents at the 3,6-positions on all repeat units of the
They also exhibit good stability to reversible oxidation under
polymer chains or on alternate repeat units of the polymer
electrolytic conditions, although they have lower ionization
chains has been realized. The effects of the methyl substit-
uents at the 3,6-positions on the polymerization reaction potentials than the homopolymers (5.2 vs 5.5 eV for the
together with the effects of the bulk of 9-alkyl substituents homopolymers). Both classes of polymers emit in the blue
on the carbazole repeat units have been discussed. Homo- part of the electromagnetic spectrum and are thermally stable
polymers with methyl substituents at the 3,6-positions on up to 350 °C. The electrolytic stability of these new classes
all carbazole repeat units, poly(3,6-dimethyl-9-alkyl-9H- of materials compared to that of 2,7-linked 9-alkylcarbazole
carbazole-2,7-diyl)s, displayed large band gaps (3.21 eV), polymers with no methyl substituents at their 3,6-positions
were found to be stable under electrolytic conditions, and should enable their effective use as stable blue-light-emitting
displayed good redox reversibility. Copolymers with methyl materials in display devices.
substituents at the 3,6-positions on alternate carbazole repeat
units, poly(3,6-dimethyl-9-alkyl-9H-carbazole-alt-9-alkyl- Acknowledgment. We acknowledge the EPSRC for finan-
9H-carbazole-2,7-diyl)s, also displayed wide band gaps, cial support of this work (Grant GR/S56719/01).
although lower than those of the homopolymers (2.95 eV).
Homopolymers P1 displayed moderate fluorescence quantum CM051305L