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Theoretical Study of the Substituent Effects on the Nonlinear Optical Properties of a Room‐Temperature‐Stable Organic Electride
Author(s) -
Sun WeiMing,
Li XiangHui,
Li Ying,
Ni BiLian,
Chen JingHua,
Li ChunYan,
Wu Di,
Li ZhiRu
Publication year - 2016
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201600970
Subject(s) - substituent , chemistry , density functional theory , nitro , polar effect , nonlinear optical , computational chemistry , photochemistry , crystallography , medicinal chemistry , organic chemistry , alkyl , nonlinear system , physics , quantum mechanics
Excess‐electron compounds can be considered as novel candidates for nonlinear optical (NLO) materials because of their large static first hyperpolarizabilities ( β 0 ). A room‐temperature‐stable, excess‐electron compound, that is, the organic electride Na@(TriPip222), was successfully synthesized by the Dye group ( J. Am. Chem. Soc . 2005 , 127 , 12416). In this work, the β 0 of this electride was first evaluated to be 1.13×10 6 au, which revealed its potential as a high‐performance NLO material. In particular, the substituent effects of different substituents on the structure, electride character, and NLO response of this electride were systemically studied for the first time by density functional theory calculations. The results revealed that the β 0 of Na@(TriPip222) could be further increased to 8.30×10 6 au by introducing a fluoro substituent, whereas its NLO response completely disappeared if one nitryl group was introduced because the nitro‐group substitution deprived the material of its electride identity. Moreover, herein the dependence of the NLO properties on the number of substituents and their relative positions was also detected in multifluoro‐substituted Na@(TriPip222) compounds.