双(取代水杨醛)间苯二甲酰腙有机锡配合物的一锅溶剂热法合成、结构和荧光性质  

One-Pot Solvothermal Synthesis,Structure,and Fluorescence Properties of Bis(substituted salicylaldehyde) m-Phthaloylhydrazone Organotin Complexes

作　　者：冯泳兰 张复兴 蒋伍玖 邝代治 FENG Yong-Lan;ZHANG Fu-Xing;JIANG Wu-Jiu;KUANG Dai-Zhi(Key Laboratory of Functional Metal-Organic Compounds of Hunan Province,Key Laboratory of Organometallic New Materials,College of Hunan Province,Hunan Provincial Engineering Research Center for Monitoring and Treatment of Heavy Metals Pollution in the Upper Reaches of Xiangjiang River,College of Chemistry and Material Science,Hengyang Normal University,Hengyang,Hunan 421008,China)

机构地区：[1]功能金属有机化合物湖南省重点实验室,金属有机新材料湖南省高校重点实验室,湘江上游重金属污染监测与治理湖南省工程研究中心,衡阳师范学院化学与材料科学学院,衡阳421008

出　　处：《无机化学学报》2022年第12期2443-2451,共9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：以间苯二甲酰肼、取代水杨醛和有机锡前体化合物进行一锅溶剂热法反应,合成了5个双(取代水杨醛)间苯二甲酰腙有机锡配合物m‑Ph(CONH—N=CH(o‑O)PhR^(1))(SnR^(2))2:R^(1)=Naphth,R^(2)=Cy(1);R^(1)=3‑t‑Bu,R^(2)=n‑Bu(2);R^(1)=5‑F,R^(2)=Ph(3);R^(1)=4‑Cl,R^(2)=Ph(4);R^(1)=3‑t‑Bu,R^(2)=Ph(5)。经元素分析、红外光谱、(1H、^(13)C和^(119)Sn)核磁共振谱表征,并用X射线衍射方法确证了配合物1~5的晶体分子结构。配合物1~4为三斜晶系P1ˉ空间群,配合物5为单斜晶系P2_(1)空间群。中心锡与配位原子组成五配位畸形三角双锥构型。将水杨醛酰腙链与有机锡配位形成远离中心苯环的构型称为“反式”,将与中心苯环取向相同的构型称为“顺式”。通过C1—C2或C4—C8单键旋转,中心苯环上的2个配位链发生构型翻转。配合物1形成“反-反”式构型,配合物2形成“顺-顺”式构型,配合物3、4和5形成“顺-反”式构型。荧光研究表明,配合物具有发光性能,特别是配合物1和4的有机溶液具有很强的荧光性能。Five bis(substituted salicylaldehyde)m‑phthaloylhydrazone organotin complexes,m‑Ph(CONH—N=CH(o‑O)PhR^(1))(SnR^(2))_(2),were synthesized by one‑pot solvothermal reaction of benzene‑1,3‑dicarbohydrazide,substituted salicylaldehydes and organotin precursors,respectively,where R^(1)=Naphth,R^(2)=Cy(1);R^(1)=3‑t‑Bu,R^(2)=n‑Bu(2);R^(1)=5‑F,R^(2)=Ph(3);R^(1)=4‑Cl,R^(2)=Ph(4);R^(1)=3‑t‑Bu,R^(2)=Ph(5).Their structures were characterized by elemental analysis,IR and 1H,^(13)C,^(119)Sn NMR,and the crystal structures of complexes 1‑5 were confirmed by X‑ray diffraction.Complexes 1‑4 belong to the triclinic P1space group and complex 5 crystallizes in the monoclinic P2_(1) space group.The central tin and the coordinated atom form a five‑coordinated distorted triangular bipyramids configuration.By C1—C2 or C4—C8 single bond rotation,the configuration of the two coordination chains on the central benzene ring is reversed.Here,it is defined that the configuration of salicylaldehyde acylhydrazone chain coordinated with organotin to form far from the central benzene ring is called“trans”,and the configuration with the same orientation as the central benzene ring is called“cis”.Therefore,complex 1 forms a“trans‑trans”configuration,complex 2 forms a“cis‑cis”configuration,and complexes 3,4 and 5 form a“cis‑trans”configuration.Fluorescence studies showed that the complexes had luminescence properties,especially the organic solutions of 1 and 4 had strong fluorescence properties.

关 键 词：双(取代水杨醛)间苯二甲酰腙有机锡 一锅溶剂热合成 晶体结构 荧光性质 

分 类 号：O614.432[理学—无机化学]