两种具有二次谐波响应的紫外透过氨基磺酸盐A(NH_(2)SO_(3))(A=Li、Na)  

A(NH_(2)SO_(3))(A=Li,Na):Two ultraviolet transparent sulfamates exhibiting second harmonic generation response

作　　者：莫翠伍 张刚敏 吴超[1] 黄智鹏 张弛[1] MO Cuiwu;ZHANG Gangmin;WU Chao;HUANG Zhipeng;ZHANG Chi(China-Australia Joint Research Center for Functional Molecular Materials,School of Chemical Science and Engineering,Tongji University,Shanghai 200092,China)

机构地区：[1]同济大学化学科学与工程学院,中澳功能分子材料联合研究中心,上海200092

出　　处：《无机化学学报》2024年第7期1387-1396,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.51432006,52002276);教育部长江学者创新团队计划(No.IRT14R23);教育部和国家外国专家局111计划(No.B13025);上海市教育委员会创新计划资助。

摘　　要：通过简便的蒸发方法得到了2种碱金属磺酸盐非线性光学(NLO)晶体,即Li(NH_(2)SO_(3))和Na(NH_(2)SO_(3))。Li(NH_(2)SO_(3))以极性空间群Pca2_(1)(编号29)结晶。Li(NH_(2)SO_(3))的结构可以描述为由[LiO_(4)]^(7-)多面体通过共角连接与NH_(2)SO_(3)-四面体相互连接而形成的三维网络。Na(NH_(2)SO_(3))以极性空间群P2_(1)2_(1)2_(1)(编号19)结晶。Na(NH_(2)SO_(3))的结构可以描述为由扭曲的[NaO_(6)]^(11-)八面体通过共角连接与NH_(2)SO_(3)-四面体相互连接而形成的三维网络。紫外可见近红外光谱表明,Li(NH_(2)SO_(3))和Na(NH_(2)SO_(3))分别具有5.25和4.81eV的大光学带隙。粉末二次谐波发生(SHG)测量显示,Li(NH_(2)SO_(3))和Na(NH_(2)SO_(3))的SHG强度分别为KH_(2)PO_(4)的0.32倍和0.31倍。第一原理计算证实,非线性光学性能主要来自氨基磺酸阴离子和碱金属氧阴离子多面体的协同作用。Two alkali-metal sulfamates nonlinear optical(NLO)crystals,Li(NH_(2)SO_(3))and Na(NH_(2)SO_(3)),have been obtained through the facile evaporation method.Li(NH_(2)SO_(3))crystallizes in the polar space group Pca2_(1)(No.29).The structure of Li(NH_(2)SO_(3))can be described as a 3D network formed by[LiO_(4)]^(7-)polyhedral connecting with NH_(2)SO_(3)^(-)tetrahedra through corner-sharing.Na(NH_(2)SO_(3))crystallizes in the polar space group P2_(1)2_(1)2_(1)(No.19).The structure of Na(NH_(2)SO_(3))can be described as a 3D network formed by distorted[NaO_(6)]^(11-)octahedral connecting with NH_(2)SO_(3)^(-)tetrahedra through corner-sharing.The UV-Vis-near-infrared spectra demonstrate that Li(NH_(2)SO_(3))and Na(NH_(2)SO_(3))possessed large optical band gaps of 5.25 and 4.81 eV,respectively.Powder second-harmonic generation(SHG)measurements demonstrate that the SHG intensity of Li(NH_(2)SO_(3))and Na(NH_(2)SO_(3))were 0.32 times and 0.31 times that of KH_(2)PO_(4),respectively.First-principles calculations confirm the nonlinear optical performance mainly derived from the synergistic effect of amino sulfonate anions and alkali metal oxide anionic polyhedra.CCDC:2339109,Li(NH_(2)SO_(3));2339110,Na(NH_(2)SO_(3)).

关 键 词：紫外非线性光学材料 带隙 二次谐波发生 第一性原理计算 

分 类 号：O614.322[理学—无机化学] O614.344[理学—化学] O614.111O614.112