【作者】 李玲；

【导师】 黄长沧；

【作者基本信息】 福州大学 ， 物理化学， 2017， 硕士

【摘要】 有机-金属卤化物越来越受到人们的广泛关注。主要是由于以下两种原因,一是由于这一类化合物具有许多物理性质,例如半导体,光致变色,热致变色,光致发光,非线性光学活性以及铁电性能等,二是由于金属卤化物具有十分丰富的结构化学。选择合适的有机组元与金属卤化物进行自组装,是决定有机-金属卤化物材料性能的关键。含氮杂环化合物作为有机组元具有一定的刚性,热稳定性和化学稳定性等特点。本论文我们选用含氮杂环化合物与金属卤化物构筑形成一系列有机金属卤化物。主要工作有以下几个部分:(1)本论文采用了溶液挥发法、溶剂热法及扩散法合成了 16个有机-金属卤化物,并通过X-射线单晶衍射仪确定了这16个化合物的晶体结构:[H2trz]2[CdCl4]化合物 1[H2trz]2[PbBr4]化合物 2[H2trz]4[Pb3I10]·2H2O 化合物 3[N-MeimH][CdC13]化合物 4[4-MeimH][Pb2I5]化合物 5[1-EtimH]2[Pb2Br6]化合物 6[1-EtimH][PbI3]化合物 7[2-EtimH]2[PbI4]·0.5I2h 化合物 8[H2mela]2[CdCl5]·cl 化合物 9[H2mela]2[CdCl5]·CI 化合物 10[H2mela][PbBr4]化合物 11[HPhmela]2[CdC14].2H2O 化合物 12[HPhmela]2[ZnC14]·2H2O 化合物 13[H2dabco]4[NH4]3[Pb5Br21]化合物 14[(C15H30N4)Cu5I7]化合物 15[(C15H30N4)2(H20)2Cd5Cl14]化合物 16(2)化合物12、13具有零维的孤立结构,通过氢键相互作用拓展为一维的链状结构;化合物4、6、7、8、9、10、16具有一维的链状结构,其中化合物6、8通过氢键相互作用拓展为二维的平面结构,化合物9、10、16则通过氢键相互作用连接构成三维的网络结构;化合物1、2、3、5、11具有二维的层状结构,其中化合物11通过氢键作用连接构成三维的网络结构;化合物14、15为三维的网络结构,其中化合物15具有二重穿插结构。(3)对合成的配体L1进行了红外光谱和核磁表征,对合成的化合物进行了 X-射线粉末衍射、红外光谱、荧光光谱和热重分析的测试与表征,对部分化合物做了固体紫外-可见光谱测试。(4)对化合物3的变色性质进行了探究,结果表明化合物3具有变色性质是由于化合物中客体分子的得失或改变;对化合物2进行了卤素离子掺杂及发光性质的研究,采用荧光光谱仪对卤素离子掺杂型化合物的荧光性能进行了研究,结果表明对卤素离子进行掺杂可以有效地调控化合物的发光性能,卤素离子掺杂型化合物的发射峰位置发生了明显的红移,发光颜色也由蓝光变为绿光。化合物9、10为同质异晶结构,对化合物9、10的晶型转变过程进行了 X-射线粉末衍射记录。对非心对称结构的化合物12和13进行了非线性光学性质研究,化合物12、13的SHG信号响应强度分别为KDP的0.6和0.3倍。更多还原

【Abstract】 The organic-metal halide has been attracting growing attention.This interest is inspired by two main reasons.The first one is related to numerous physical properties demonstrated by the members of this class of compounds,for example,semiconductivity,photochromism,thermochromism,luminescence,nonlinear optical activity,ferroelectricity,etc.The second point is related to the structural diversity of the metal halide.The key to organic-metal halide material properties is choosing suitable organic components and metal halide to self-assembly.Nitrogen heterocyclic compounds as organic element have certain rigidity,thermal stability and chemical stability.In this work,we use the nitrogen heterocyclic compounds and metal halides to form a series of organic-metal halides.The studied works are concluded in the following:(1)In this paper,we using volatilization,solvothermal and diffusion method to bulid sixteen organic-metal halide.All of the complexes were determined by X-ray single crystal diffractive technology.[H2trz]2[CdCl4]Complex 1[H2trz]2[PbBr4]Complex 2[H2trz]4[Pb3I10]2H20 Complex 3[N-MeimH][CdCl3]Complex 4[4-MeimH][Pb2I5]Complex 5[1-EtimH]2[Pb2Br6]Complex 6[1-EtimH][PbI3]Complex 7[2-EtimH]2[PbI4]·0.5I2 Complex 8[H2mela]2[CdCl5]·Cl Complex 9[H2mela]2[CdCl5]Cl Complex 10[H2mela][PbBr4]Complex 11[HPhmela]2[CdCl4]·2H2O Complex 12[HPhmela]2[ZnCl4]·2H2O Complex 13[H2dabco]4[NH4]3[Pb5Br2i]Complex 14[(C15H3oN4)Cu5I7]Complex 15[(Ci5H3oN4)2(H2O)2Cd5Cl14]Complex 16(2)Complexes 12、13 exhibit 0-D structures and the 0-D structures of complexes 12、13 are further extended into 1-D chains via hydrogen bonds.Complexes 4、6、7、8、9、10、16 display 1-D chain structures.And the 1-D chain structures of complexes 6、8 are further extended into 2-D networks via hydrogen bonds.The 1-D chain structures of complexes 9、10、16 are further extended into 3-D networks via hydrogen bonds,wherein complexes 9、10 are the allomorphism.Complexes 1、2、3、5、11 exhibit 2-D layered structures,and the 2-D layered structures of complexes 11 is further extended into 3-D networks via hydrogen bonds.Complex 14 and 15 show 3-D network structures,meanwhile complex 15 is 2-fold interpenetrated structure.(3)The ligand L1 has been characterized by IR and NMR.The complexes have been further characterized by X-Ray powder diffraction,IR spectra,fluorescent spectra and TG analysis.UV-vis spectra is carried out on part of the complexes.(4)The allochromasia properties of complex 3 has been investigated,and it turned out that the allochromasia of complex 3 was owing to the gain,loss or change of guest molecule.The halide ions doping and luminescence properties for complex 2 have been researched.And the doped complexes were characterized by fluorescent spectra.Results show halide ions doped can effectively regulate the luminescent properties of complexes and the emission peak position considerably red-shifted.The fluorescent color changed from blue to green light.Complexes 9、10 show the allomorphic structure.Transformation of the two polymorphs were recorded by X-Ray powder diffraction.In addition,complexes 12、13 poss non symmetrical structures,and nonlinear optical behavior measurement of the samples indicated that the complexes 12、13 display SHG response approximately 0.6,0.3 times that of KDP.更多还原