Yang Yuanyu, Xiao Yan, Li Bingxuan, Chen Yi-Gang, Guo Penghui, Zhang Bingbing, Zhang Xian-Ming
Key Laboratory of Magnetic Molecules and Magnetic Information Material of Ministry of Education, School of Chemistry and Material Science, Shanxi Normal University, Taiyuan 030031, China.
College of Chemistry and Materials Science, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, Chemical Biology Key Laboratory of Hebei Province, Hebei University, Baoding 071002, China.
J Am Chem Soc. 2023 Oct 18;145(41):22577-22583. doi: 10.1021/jacs.3c07547. Epub 2023 Oct 9.
Atoms in special lattice sites can play a crucial role in realizing materials properties, which is long pursued but difficult to control. Herein, by adopting a stereochemically active lone-pair-containing metal substitution strategy, a nonlinear-optical (NLO) silicate crystal Li(OH)PbSiO was successfully synthesized, featuring [PbSiO] layers with the perfect orientation of the stereochemically active lone-pair Pb(II) cation in the polar-axis lattice. Li(OH)PbSiO overcomes the long-standing problem of silicates, that is, poor nonlinear properties because it exhibits both the largest birefringence of 0.082 and the largest phase-matchable second-harmonic-generation (SHG) efficiency of 21 × KDP among the known silicates. The successful polar-axis lattice substitution could offer a new direction for realizing the rational control of materials structures and properties.
处于特殊晶格位置的原子在实现材料性能方面可发挥关键作用，这是长期以来一直追求但难以控制的。在此，通过采用含立体化学活性孤对电子的金属取代策略，成功合成了一种非线性光学（NLO）硅酸盐晶体Li(OH)PbSiO，其[PbSiO]层中立体化学活性孤对电子Pb(II)阳离子在极轴晶格中具有完美取向。Li(OH)PbSiO克服了硅酸盐长期存在的问题，即非线性性能较差，因为在已知硅酸盐中，它展现出0.082的最大双折射以及21×KDP的最大可相位匹配二次谐波产生（SHG）效率。成功的极轴晶格取代可为实现材料结构和性能的合理控制提供新方向。
