双(3⁃乙氧基水杨醛)缩间苯二甲酰腙四丁(苯)基二锡的合成、结构和荧光性质  

Synthesis,Structure and Fluorescence Properties of Bis(3⁃ethoxysalicylaldehyde)1,3⁃Benzyldiacyl Hydrazone Tetrabutyl(phenyl)ditin

作　　者：冯泳兰 王莹 蒋伍玖 庾江喜 张复兴 邝代治 FENG Yong-Lan;WANG Ying;JIANG Wu-Jiu;YU Jiang-Xi;ZHANG Fu-Xing;KUANG Dai-Zhi(Key Laboratory of Functional Metal‑Organic Compounds of Hunan Province,Key Laboratory of Functional Organometallic Materials,University of Hunan Province,College of Chemistry and Material ScienceHengyang Normal University,Hengyang,Hunan 421008,China)

机构地区：[1]衡阳师范学院化学与材料科学学院,功能金属有机化合物湖南省重点实验室,功能金属有机材料湖南省普通高等学校重点实验室,衡阳421008

出　　处：《无机化学学报》2022年第1期103-110,共8页Chinese Journal of Inorganic Chemistry

基　　金：功能金属有机化合物湖南省重点实验室资助。

摘　　要：在乙醇溶液中以3⁃乙氧基水杨醛和间苯二甲酰肼反应,制备双(3⁃乙氧基水杨醛)缩间苯二甲酰腙(H_(4)L)配体。用H_(4)L分别与二丁基氧化锡和三苯基氢氧化锡甲醇溶剂热反应,合成了双(3⁃乙氧基水杨醛)缩间苯二甲酰腙四丁(苯)基二锡配合物:Bu_(4)Sn_(2)L(T1)和Ph_(4)Sn_(2)L(T2)。用元素分析、红外光谱、紫外可见光谱、核磁共振谱以及单晶X射线衍射表征了H_(4)L和配合物的结构。H_(4)L的分子式为C_(26)H_(26)N_(4)O_(6),晶体属单斜晶系C2/c空间群,2个甲酰肼缩(3⁃乙氧基)水杨醛呈顺式对称构型。T1的分子式为C_(42)H_(58)N_(4)O_(6)Sn_(2),晶体属正交晶系Pbcn空间群,H_(4)L的2个甲酰肼缩(3⁃乙氧基)水杨醛链向内翻转180°,配位原子与锡配位构成畸形三角双锥构型,分子结构关于C2…C4轴对称。T2的分子式为C_(50)H_(42)N_(4)O_(6)Sn_(2),晶体属三斜晶系P1空间群,配体的一个甲酰肼缩(3⁃乙氧基)水杨醛保持原构型,另一个甲酰肼缩(3⁃乙氧基)水杨醛向内翻转180°,形成2个不同构型取向的配位链,分别与二苯基锡配位形成反式双核不对称畸形三角双锥构型的配合物。H_(4)L、T1、T2的氯仿溶液(50μmol·L^(-1))的荧光光谱表明:H_(4)L在520 nm有弱荧光,T1和T2在518 nm具有比配体强14~15倍的荧光发射峰。The bis(3⁃ethoxysalicylaldehyde)1,3⁃benzyldiacyl hydrazone(H_(4)L)ligand was prepared by the reaction of 3⁃ethoxysalicylaldehyde with benzene⁃1,3⁃dicarbohydrazide in ethanol solution.Bis(3⁃ethoxysalicylaldehyde)1,3⁃benzyldiacyl hydrazone tetrabutyl(phenyl)ditin,Bu_(4)Sn_(2)L(T1)and Ph_(4)Sn_(2)L(T2),were synthesized by solvothermal reaction of H_(4)L with dibutyltin oxide and triphenyltin hydroxide in methanol,respectively.The structures of ligand and complexes were characterized by elemental analysis,IR,UV⁃Vis spectroscopy,NMR,and single⁃crystal X⁃ray diffraction.The molecular formula of H_(4)L is C_(26)H_(26)N_(4)O_(6).The crystal of H_(4)L belongs to the monoclinic system and space group C2/c.Two formylhydrazide(3⁃ethoxy)salicylaldehydes are cis⁃symmetric configuration.The molecular formula of T1 is C_(42)H_(58)N_(4)O_(6)Sn_(2).The crystal of T1 belongs to the orthorhombic system and space group Pbcn.The two formylhydrazide(3⁃ethoxy)salicylaldehyde chains of H_(4)L turn inward 180°,and a distorted trigonal bipyramid is formed by the coordination of coordinating atoms with tin.The molecular structure is axis⁃symmetric about C2…C4.The molecular formula of T2 is C_(50)H_(42)N_(4)O_(6)Sn_(2).The crystal of T2 belongs to the triclinic system,space group P1.One formylhydrazide(3⁃ethoxy)salicylaldehyde of H_(4)L keeps the original configuration,and the other formylhydra⁃zide(3⁃ethoxy)salicylaldehyde turns inward 180°.Two coordination chains with different configuration orientations were formed,which coordinated with diphenyltin to form a binuclear trans⁃asymmetric distorted trigonal bipyramid complexes.The fluorescence properties of trichloromethane solutions of H_(4)L,T1,T2(50μmol·L^(-1))were tested.The results showed that H_(4)L had weak fluorescence at 520 nm,and T1 and T2 had 14⁃15 times stronger fluorescence emission peaks than the ligand at 518 nm.CCDC:2092625,H_(4)L;2092626,T1;2092627,T2.

关 键 词：双(3⁃乙氧基水杨醛)缩间苯二甲酰腙 有机锡配合物 溶剂热合成 晶体结构 荧光性质 

分 类 号：O614.432[理学—无机化学]