Song Yunxia, Luo Min, Liang Fei, Ye Ning, Lin Zheshuai
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
Chem Commun (Camb). 2018 Feb 6;54(12):1445-1448. doi: 10.1039/c7cc08863a.
Molecular construction with π-conjugated groups is a favorable strategy to discover superior nonlinear optical (NLO) materials. Herein, a novel vanadium-carbonate compound K[V(O)O]CO (KVCO), which combines two different π-orbital groups, delocalized (CO) π-orbital groups and localized (O) π-orbital groups, was synthesized. Benefiting from the well-arranged [V(O)OCO] unit and dual-synergistic π-d-π interaction, KVCO has the largest second harmonic generation (SHG) effect (about 20 times that of KDP) among the current carbonate NLO materials. Moreover, first-principles calculation elucidated the coupling enhancement mechanism between (CO), (O) and VO groups.
构建含有π共轭基团的分子是发现优质非线性光学（NLO）材料的一种有效策略。在此，合成了一种新型钒碳酸盐化合物K[V(O)O]CO（KVCO），它结合了两种不同的π轨道基团，即离域的（CO）π轨道基团和定域的（O）π轨道基团。得益于排列有序的[V(O)OCO]单元以及双协同π-d-π相互作用，KVCO在目前的碳酸盐NLO材料中具有最大的二次谐波产生（SHG）效应（约为KDP的20倍）。此外，第一性原理计算阐明了（CO）、（O）和VO基团之间的耦合增强机制。
