Abstract
Semi-empirical AM1 and ZINDO/S, as well as density function theory (DFT) method B3LYP/6-31G(d) quantum chemical calculations were carried out to study the electronic structures and optical properties of poly(p-phenylene vinylene) derivatives (PPVs) with 10 and 11 phenylene rings in the backbone. The calculations suggest that the assembly of alternate incorporation of CN and alkoxy substituted phenylene rings in the PPV backbone could be a good way to construct organic semiconductors with low HOMO/LUMO energy band-gaps. The effect of the end-group on the electronic structures and optical properties of the conjugated polymer was investigated by the calculated UV-Vis and UPS spectra. It was demonstrated that the aldehyde and phosphate end-groups have limited effects on the photophysical properties in the UV-visible range.
Similar content being viewed by others
References
Burroughes JH, Bradley DDC, Brown AR, Marks RN, Mackay K, Friend RH, Burn PL, Holmes AB. Electroluminescence in conjugated polymers. Nature, 1990: 347: 539–540
Heeger AJ. Semiconducting polymers: The Third Generation. Chem Soc Rev, 2010, 39(7): 2354–2371
Bian LY, Zhu EW, Tang J, Tang WH, Zhang FJ. Recent progress in the design of narrow bandgap conjugated polymers for high-efficiency organic solar cells. Prog Polym Sci, 2012, 37: 1292–1331
Tekin E, Egbe DA, Kranenburg JM, Ulbricht C, Rathgeber S, Birckner E, Rehmann N, Meerholz K, Schubert US. Effect of side chain length variation on the optical properties of PPE-PPV hybrid polymers. Chem Mater, 2008, 20(8): 2727–2735
Mbarek M, Zaidi B, Alimi K. Theoretical study of the alkoxyls groups effect on PPV-ether excited states, a relationship with femtosecond decay. Spectrochim Acta Part A, 2012, 88: 23–30
Hubijar E, Papadimitratos A, Lee D, Zakhidov A, Ferraris JP. Synthesis and characterization of a novel symmetrical sulfonesubstituted polyphenylene vinylene (SO2EH-PPV) for applications in light emitting devices. J Phys Chem B, 2013, 117: 4442–4448
Yang SH, Wu CC, Lee CF, Liu MH. Synthesis and luminescence of red MEH-PPV:P3OT polymer. Displays, 2008, 29(3): 214–218
Tinti F, Sabir FK, Gazzano M, Righi S, Ulbricht C, Usluer O, Pokorna V, Cimrova V, Yohannes T, Egbe D, Camaioni N. Tuning the properties of an anthracene-based PPE-PPV copolymer by fine variation of its macromolecular parameters. RSC Adv, 2013, 3: 6972–6980
Egbe DA, Tekin E, Birckner E, Pivirikas A, Sariciftci NS, Schubert US. Effect of styryl side groups on the photophysical properties and hole mobility of PPE-PPV systems. Macromolecules, 2007, 40: 7786–7794
Gunes S, Neugebauer H, Sariciftci NS. Conjugated polymer-based organic solar cells. Chem Rev, 2007, 107(4): 1324–1338
Belletete M, Morin JF, Leclerc M, Durocher G. A theoretical, spectroscopic, and photophysical study of 2,7-carbazolenevinylene-based conjugated derivatives. J Phys Chem A, 2005, 109, 6953-6959
Xiao Y, Yu W L, Chen ZK, Lee NHS, Lai YH, Huang W. Synthesis and characterization of a novel light-emitting copolymer with improved charge-balancing property. Thin Solid Film, 2000, 363: 102–103
Bartha F, Howard IA, Geerlings P, Alsenoy CV, Vanderzande D, Cleij T J, Bogar F. Density functional crystal orbital study of cyano-substituted poly(para-phenylene-vinylene) and poly-(quinoxaline-vinylene). Int J Quantum Chem, 2006, 106: 1912–1923
Garcia JR, Peres LO, Fernandes MR, Gruber J, Nart FC. One-step electrochemical synthesis of pure poly(2,5-dicy-ano-p-phenylene-vinylene) films. J Solid State Electrochem, 2004, 8: 122–126
Zheng C, Tao Y, Cao JZ, Chen RF, Zhao P, Wu XJ, Huang W. The structural, electronic, and optical properties of ladder-type polyheterofluorenes: A theoretical study. J Mol Model, 2012, 18(11): 4929–4939
May F, Al-Helwi M, Baumeier B, Kowalsky W, Fuchs E, Lennartz C, Andrienko D. Design rules for charge-transport efficient host materials for phosphorescent organic light-emitting diodes. J Am Chem Soc, 2012, 134: 13818–13822
Chang R, Hsu JH, Fann WS, Liang KK, Chang CH, Hayashi M, Yu J, Lin SH, Chang EC, Chuang K R, Chen SA. Experimental and theoretical investigations of absorption and emission spectra of the light-emitting polymer MEH-PPV in solution. Chem Phys Lett, 2000, 317: 142–152
Giro R, Caldas MJ, Galvao DS. Band gap engineering for poly(p-phenylene) and poly(p-phenylene vinylene) copolymers using the tight-binding approach. Int J Quantum Chem, 2005, 103(5): 588–596
Ivanovic N, Radisavljevic I, Marjanovic D, Bojanic S, Carreras C. Molecular size and conformational effects on oligophenylene’s electronic and vibrational properties, J Polym Sci Pol Phys, 2006, 44(13): 1783–1794
Chen RF, Ma C, Pan JF, Zheng C, Huang W. Theoretical study of the electronic ground states and low lying singlet excited states of thiophene-based spirofluorenes; Sci China Phys, Mechan & Astron. 2011, 54(5): 884–889
Cornil J, Dos SD, Beljonne D, Bredas JL. Electronic structure of phenylene vinylene oligomers: Influence of donor/acceptor substitutions. J Phys Chem, 1995, 99(15): 5604–5611
Feng DD, Wang SF, Zhuang QX, Wu PP, Han ZW. Semi-empirical calculation and spectroscopic study of protonated poly(p-phenylene benzobisoxazole) models. Polymer, 2004, 45(26): 8871–8879
Zerner MC. Semiempirical molecular orbital methods. Reviews in Computational Chemistry, Volume 2, Chapter 8, 313–365. Lipkowitz KB, Boyd DB, Eds. VCH Publishers, Inc. 1991
Hyperchem 4.5, 1995 Hypercube, Inc.
AMPAC Version 6.55, Semichem, Inc., PO Box 1649, Shawnee KS 66222
Ziegler T. Approximate density functional theory as a practical tool in molecular energetics and dynamics, Chem Rev, 1991, 91(5): 651–667
Meng S, Jiang J, Wang Y, Ma J. Modulation of electronic structures of thienylene vinylene oligomers by substituents and solvents: Ground and excited states. J Phys Org Chem, 2009, 22: 670–679
Chen RF, Zhu R, Zheng C, Fan QL, Huang W. Synthesis, characterization, and applications of vinylsilafluorene copolymers: New host materials for electroluminescent devices. Sci China Chem, 2011, 53(11): 2329–2336
Tiradorives J, Jorgensen WL. Performance of B3LYP density functional methods for a large set of organic molecules. J Chem Theo Comput, 2008, 4: 297–306
Yin J, Chen RF, Zhang SL, Li HH, Zhang GW, Feng XM, Ling QD, Huang W. Theoretical study of charge transfer properties of the π-stacked poly(1,1-silafluorene)s. J Phys Chem C, 2011, 115(30):14778–14785
Ma J, Li SH, Jiang YS. A time-dependent DFT study on band gaps and effective conjugation lengths of polyacetylene, polyphenylene, polypentafulvene, polycyclopentadiene, polypyrrole, polyfuran, polysilole, polyphosphole, and polythiophene. Macromolecules, 2002, 35(3): 1109–1115
Cornil J, Beljonne D, Heller CM, Campbell IH, Laurich BK, Smith DL, Bradley DDC, Mullen K, Bredas JL. Photoluminescence spectra of oligo-paraphenyllenevinylenes: A joint theoretical and experimental characterization, Chem Phys Lett, 1997, 278:139–145
Cornil J, Vanderdonckt S, Lazzaroni R, dos Santos DA, Thys G, Geise HJ, Yu LM, Szablewski M, Bloor D, Logdlund M, Salaneck WR, Gruhn NE, Lichtenberger DL, Lee PA, Armstrong NR, Bredas JL. Valence electronic structure of pi-conjugated materials: Simulation of the ultraviolet photoelectron spectra with semiempirical Hartree-Fock approaches. Chem Mater, 1999, 11: 2436
Lhost O, Bredas JL, Graham SC, Friend RH, Bradley DDC. Theoretical study of the electronic structure of poly(2,5-dimethoxypara-phenyl-enevinylene) and its oligomers. Synth Met, 1993, 57(2-3): 4290–4295
Fahlman M, Loegdlund M, Stafstroem S, Salaneck WR, Friend RH, Burn PL, Holmes AB, Kaeriyama K, Sonoda Y, Meyers F, Bredas JL. Experimental and theoretical studies of the electronic structure of poly(p-phenylenevinylene) and some ring-substituted derivatives. Macromolecules, 1995, 28(6): 1959–1965
Adamo C, Barone V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J Chem Phys, 1999, 110:6158–617
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Zheng, C., Pan, J., Chen, R. et al. Theoretical investigation of substitution and end-group effects on poly(p-phenylene vinylene)s. Sci. China Chem. 57, 435–441 (2014). https://doi.org/10.1007/s11426-013-4996-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-013-4996-4