Abstract: The low bandgap conjugated polymer with electron donor (D)-electron acceptor (A) units is a novel semiconducting material, which has been paid close attention to and studied extensively in the past 20 years. The chain structure and composition of D-A type low bandgap polymer directly determine its physical properties such as optical, electrochemistry, electronic and so on. 4,5-diamino-orthodicyanide benzene is a 2-dimension charge-transferring molecule and has unique physical properties because there are two electron-donating groups (-NH2) and two electron-withdrawing groups (-CN) and they are bonded to the same aromatic ring at para-position, respectively. In this work, tetrabutylammonium tetrafluoroborate dissolved in acetonitrile/water solution was used as an electrolyte, electrochemical oxidation polymerizes of 4,5-diamino-orthodicyanide benzene was carried out using cyclic voltammetry(CV) and the polymer films were deposited on ITO glass electrode surface. Their crystal structure, morphology, thermal properties were characterizated, and the electron energy levels (HOMO/LUMO) and energy gap were calculated for the deposited polymers by testing their electrochemical and optical properties. An optimized electrochemical polymerization condition was concluded for 4,5-diamino-orthodicyanide benzene monomer based on the study that the effect of acetonitrile/water volume ratio in electrolyte, CV scanning rate, CV scanning cycle on electrochemical polymerization of the monomer and on the structures and properties of the deposited polymer, and a novel N-type organic semi-conductor D-A conjugated polymer with low bandgap, perfect crystalline morphology and high thermal stability was successfully prepared.
1 Wang C L, Dong H N, Hu W P, et al. Chemical Review, 2012, 112 (4), 2208. 2 Choi M C, Kim Y, Ha C S. Progress in Polymer Science, 2008, 33(6), 581. 3 Zhong W K, Li K, Cui J, et al. Macromolecules, 2017, 50(20), 8149. 4 Jou J H, Kumar S, Agrawal A, et al. Journal of Materials Chemistry C, 2015, 3(14), 2974. 5 Zhang X, Shen F, Hu Z C, et al. ACS Sustainable Chemistry & Engineering, 2019, 7(4), 4128. 6 Wang C H, Evgueni E E. Chemical Communications, 2019, 55(61), 8955. 7 Zhang S Q, Zhao Y W, Du X W, et al. Small, DOI:10.1002/smll.201805196. 8 Guo X, Martin Baumgarten, Klaus Müllen. Progress Polymer Science, 2013, 38(12), 1832. 9 Yamamoto T, Zhou Z H, Kanbara T, et al. Journal of the American Chemical Society, 1996, 118(43), 10389. 10 Jenekhe S A, Lu L, Alam M M. Macromolecules, 2001, 34(21), 7315. 11 Chochos C L, Choulis S A. Progress Polymer Science, 2011,36(10), 1326. 12 Ashwini A K, Jenekhe S A. Chemical Materials, 1996,8(2), 579. 13 Melianas A, Kemerink M. Advanced Materials, 2019, 31(22), 1806004. 14 Huang W C, Cheng P, Yang Y M, et al. Advanced Materials, 2018, 30(8), 1705706. 15 Savoie B M, Dunaisky S, Marks T J, et al. Advanced Energy Materials, 2015, 5(3), 1400891. 16 Coropceanu V, Brédas J L. Nature Materials, 2006, 5(12), 929. 17 Zhou G D, Guo K X, Li G P, et al. Diffraction of Crystals and Quasicrystals (Second Edition), Peking University Press, China, 2013(in Chinese). 周公度,郭可信,李根培, 等. 晶体和准晶体的衍射(第二版), 北京大学出版社, 2013. 18 Liu X H, Zhang C Y, Guo W C, et al. Journal of Enzyme Inhibition & Medicinal Chemistry, 2009, 24(2), 545. 19 Song J S, Zhang C, Li C H, et al. Journal of Polymer Science, Part A:Polymer Chemistry, 2010, 48(12), 2571. 20 Silver B R, Holub K, Marcek V. Electroanalytical Chemistry, 2014,731, 107. 21 Shi M L. AC impedance spectrum principle and application, National Defense Industry Press, China, 2001(in Chinese). 史美伦.交流阻抗谱原理及应用, 国防工业出版社, 2001. 22 Onwudiwe D C, Arfin T, Strydom C A, et al. Electrochimica Acta, 2013, 104, 19. 23 Chen C F, Jiang R J, Zhang G A, et al. Acta Physico-Chimica Sinica, 2009,25(3), 463(in Chinese). 陈长风, 姜瑞景, 张国安, 等. 物理化学学报, 2009, 25(3), 463. 24 Tauc J, Grigomvici R, Vancu A. Physica Status Solidi, 1966, 3(1), 37. 25 Tauc J, Abeles F. Optical properties of solids, North-Holland Publishing, Holland, 1972.