Unique Unilateral-Chelated Mode-Induced d-p-π Interaction Enhances Second-Harmonic Generation Response in New Ln3LiMS7 Family

被引：29

作者：

Yang, Ya ^{[1
]}

Chu, Yu ^{[2
]}

Zhang, Bingbing ^{[1
]}

Wu, Kui ^{[1
]}

Pan, Shilie ^{[2
]}

机构：

[1] Hebei Univ, Coll Chem & Environm Sci, Key Lab Analyt Sci & Technol Hebei Prov, Key Lab Med Chem & Mol Diag,Minist Educ, Baoding 071002, Peoples R China

[2] Chinese Acad Sci, Xinjiang Key Lab Elect Informat Mat & Devices, Xinjiang Tech Inst Phys & Chem, CAS Key Lab Funct Mat & Devices Special Environm, Urumqi 830011, Peoples R China

来源：

CHEMISTRY OF MATERIALS | 2021年 / 33卷 / 11期

基金：

中国国家自然科学基金;

关键词：

NONLINEAR-OPTICAL MATERIALS; METAL CHALCOGENIDES; MID-IR; CRYSTALS; SN; GE; SEMICONDUCTORS; RE=LA; SE; RE;

D O I：

10.1021/acs.chemmater.1c01133

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Multiple chelated configurations of anionic groups offer a great chance to design new nonlinear optical (NLO) materials with excellent performances for infrared (IR) application. In this work, the new polar Ln(3)LiMS(7) (Ln = rare-earth; M = Ge, Sn) family as promising IR NLO candidates were successfully designed and synthesized by the unique close-ring combination between LnS(8) and MS4 ligands. Note that La3LiGeS7 and La3LiSnS7 exhibit the good NLO effects (0.7 vs 1.2 x benchmark AgGaS2) with phase-matching behavior and high laser damage thresholds (6.0 vs 2.5 X AgGaS2), respectively. First-principles calculation indicates that their NLO effects originate from the synergistic effect of intrinsic dipole moments and d-p delocalized-pi electron-induced dipole oscillations in the Ln(3)LiMS(7) family. This result also verifies that unique unilateral-chelated configuration induced d-p-pi interactions are beneficial to improve the NLO performances, which offers us one feasible way (incorporation of Ln-centered ligands into crystal structure) to design new promising IR NLO materials.

引用

页码：4225 / 4230

页数：6