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Understanding the Electronic Structure of Larger Azaacenes through DFT Calculations
Author(s) -
Gao Junkuo,
Zhang Qichun
Publication year - 2014
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201400003
Subject(s) - diradical , chemistry , open shell , singlet state , ground state , density functional theory , electronic structure , computational chemistry , shell (structure) , chemical physics , atomic physics , excited state , organic chemistry , materials science , physics , composite material
Although azapentacenes have been widely demonstrated as promising candidates for n‐type organic semiconductor devices, the exploration of larger azaacenes is still a challenge. In particular, theoretical studies on the electronic structures of larger azaacenes and the influence of N substitution on the ground states are still rare. Herein, we reported our investigation on the electronic ground‐state characters of larger azaacenes through density functional theory (DFT) calculations. Our results indicated that larger azaacenes (fused aromatic rings larger than 6) would show open‐shell singlet biradical characters and the introduction of more N atoms into the backbone of large acenes could favor their closed‐shell ground states. Interestingly, azahexacenes with three or more N atoms (compounds N64–N68) and azaheptacenes (compound N74) with fourteen N atoms displayed closed‐shell singlet ground states compared with the open‐shell singlet diradical ground states for larger acenes. Our theoretical studies may guide the design and synthesis of larger azaacenes, which are the promising n‐type organic semiconducting materials.