Noncentrosymmetric Rb<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> vs Centrosymmetric Cs<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub>
Yunqiao Guo (11450835)Die Zhang (10185922)Ting Zheng (608653)Ling Huang (51752)Daojiang Gao (4284541)Jian Bi (4284544)Guohong Zou (1840012)
Abstract
Two new alkali metal formic-borates\nnamed Rb<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> and Cs<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> have\nbeen successfully synthesized under mild conditions. Influenced by\nthe different cation sizes, these two stoichiometrically equivalent\ncompounds reveal discrepant symmetries: Rb<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> is noncentrosymmetric (NCS)\nwhile Cs<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> is centrosymmetric (CS). Especially, these two title\ncompounds exhibit unique planar [(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub>]<sup>3–</sup> layers constructed from\ntwo kinds of planar π-conjugated asymmetric BO<sub>3</sub> and\nCOOH units, which induce the large birefringence, 0.09@1064 nm for\nRb<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub> and 0.10@1064 nm for Cs<sub>3</sub>(COOH)<sub>3</sub>(H<sub>3</sub>BO<sub>3</sub>)<sub>2</sub>, respectively. Optical property\nmeasurements indicate that these two compounds display short UV absorption\nedges, suggesting that they are promising short-wave UV birefringent\nmaterials. A detailed theoretical analysis confirmed that the excellent\nlinear optical property was derived from the synergistic effect of\nthe two kinds of π-conjugated planar groups.
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