Crystal structure and ON-OFF polymerization mechanism of poly(1,4-phenyleneazine-N,N-dioxide), a possible wide bandgap semiconductor

0538251 - ÚOCHB 2022 RIV GB eng J - Článek v odborném periodiku
Gallo, G. - Mihanović, A. - Rončević, Igor - Dinnebier, R. - Vančik, H.
Crystal structure and ON-OFF polymerization mechanism of poly(1,4-phenyleneazine-N,N-dioxide), a possible wide bandgap semiconductor.
Polymer. Roč. 214, Feb 1 (2021), č. článku 123235. ISSN 0032-3861. E-ISSN 1873-2291
Výzkumná infrastruktura: e-INFRA CZ - 90140
Institucionální podpora: RVO:61388963
Klíčová slova: optoelectronics * C-nitroso compounds * X-ray powder diffraction
Obor OECD: Organic chemistry
Impakt faktor: 4.432, rok: 2021
Způsob publikování: Omezený přístup
https://doi.org/10.1016/j.polymer.2020.123235

Crystal and molecular structure of poly(1,4-phenyleneazine-N,N-dioxide) (PDNB, 1), obtained from polymerization of 1,4-dinitrosobenzene, is investigated by X-ray powder diffraction (XRPD) and DFT calculations. Starting with the determined crystal structure, we have calculated the electronic structure of the polymer, which reveals that 1 is potentially a wide-bandgap (WBG) semiconductor with a band gap of 2.3 eV. Its calculated electronic spectrum with the absorbance at 400 nm is in good agreement with the experimental data. A highly organized crystal structure with linear chains of polymer indicates possible anisotropic electronic properties that could be useful in molecular photoelectronics (e.g OLEDs). Photolysis of 1 at cryogenic temperatures yields dinitrosobenzene monomers, which re-polymerize at higher temperatures. After this reversible photo-thermal cycle, the starting polymorph of 1 is recovered. Thermal analysis (TG/DSC/DTA) and in situ XRPD measurements show the high thermal stability of 1 until around 150 °C.
Trvalý link: http://hdl.handle.net/11104/0316077