【作者】 李春红；

【导师】 于杰辉；

【作者基本信息】 吉林大学 ， 无机化学， 2022， 硕士

【摘要】 无机有机杂化材料因其结构多样性,无机和有机组分所赋予的独特性质,以及它们相互作用所产生的潜在应用前景,在近几十年来得到了广泛的研究。金属-卤素（拟卤素）化合物是一类重要的杂化功能材料,特别是金属碘酸盐化合物由于其结构可调、金属对碘阴离子具有很强的亲和力以及其各种性质（如光致发光、光/热致变色、磷光、白光和光催化等）而受到人们的特别关注。为了得到更多的结构新颖和性能优异的杂化金属碘酸盐,在本论文中我们选择了不同的双（三）唑有机配体与Ag（Ⅰ）,Pb（Ⅱ）,Cu（Ⅰ）利用水热（溶剂热）方法构筑了9例杂化金属碘酸盐化合物,并对其进行单晶结构和性能方面的探究。本论文共分为五章:第一章为绪论部分,主要介绍了无机有机杂化材料的概念,发展,分类研究进展以及各领域的潜在应用。说明了本论文的选题的目的,主要研究内容和研究成果。第二章为实验方法,试剂和仪器。第三章利用了两个唑类衍生物（dtb=1,4-双（1H-1,2,4-三唑-1-基）苯,mimb=1,2-双（（2-甲基-1H-咪唑-1-基）甲基）苯）与AgI在溶剂热条件下合成了两例银碘酸盐化合物[pbmt]_0.5[AgI₂]1和[H₂（mimb）]_0.5[Ag₂I₃]2。其中1中的[pbmt]²⁺是由dtb与甲醇发生原位N-烷基化得到的。1为1-D链状结构,而2为一个特殊的三维开放框架结构。性能分析表明1在室温发黄光,在低温下不同的激发波长发黄光和黄绿光,即1具有荧光光（热）致变色性能,而2不具有这些性能。第四章选择4个唑类衍生物（mimb=1,2-双（（2-甲基-1H-咪唑-1-基）甲基）苯,1,3-bimb=1,3-双（（2-甲基-1H-咪唑-1-基）甲基）苯,1,2-bimb=1,2-双（（1H-咪唑-1-基）甲基）苯,dtb=1,4-双（1H-1,2,4-三唑-1-基）苯）与PbI₂和HI在不同的醇类溶剂中进行溶剂热反应,生成4种新的杂化铅碘酸盐化合物[H₂（mimb）][Pb₂I₆]3,[pmbmi][Pb₂I₆]4,[N,N-pmbmi][Pb₂I₆]5和[pbmt][Pb₂I₆]6。化合物4-6中的[pmbmi]²⁺,[N,N-pmbmi]²⁺,[pbmt]²⁺是由有机碱与甲醇发生原位N-烷基化反应得到的。光学性能表明3-5在低温时发黄光或红光,在室温时不发光。并且通过光催化降解染料的探究发现3具有优异的光催化性能。第五章利用了两个有机配体（dtb=1,4-双（1H-1,2,4-三唑-1-基）苯,dip=3,5-双（1H-咪唑-1-基）吡啶）在水热法和溶剂热法的条件下与Cu I合成了三例不同结构的铜碘酸盐化合物[pbmt]_0.5[Cu I₂]7,[peti][Cu I₂]I.H₂O 8和[dip（Cu₃I₃）]9。其中[pbmt]²⁺是由dtb与甲醇发生原位N-甲基化反应得到的,[peti]²⁺是dtb与甲醇发生原位N-乙基化得到的。发光性能表明9在室温时发橙光,低温时发红光,即9具有热致变色性能。更多还原

【Abstract】 Inorganic-organic hybrid materials have been extensively studied in recent decades due to their structural diversity and unique properties conferred by inorganic and organic components,as well as their potential applications arising from their interactions.Metal-halogen（pseudohalogen）compounds are an important class of hybrid functional materials,especially hybrid iodates due to their tunable structures,the strong affinity of metals for iodide anions,and their various properties such as photoluminescence,photo/thermochromic,phosphorescence,white light and photocatalysis,etc)have received special attention.In order to obtain more hybrid metal iodates with novel structures and excellent properties,in this paper,we selected different bis（tri）azole organic ligands with Ag（Ⅰ）,Pb（Ⅱ）,Cu（Ⅰ）.Nine examples of hybrid metal iodates were constructed by hydrothermal（solvothermal）method,and their single crystal structures and properties were investigated.Thesis is divided into five chapters:The first chapter is the introduction,which mainly introduces the concept,development,classification and research progress of inorganic-organic hybrid materials and potential applications in various fields.The purpose of the topic selection,main research contents and research results of this thesis are introduced.The second chapter for experiments,reagents and instruments.The third chapter utilizes two azole molecules,dtb=1,4-bis（1H-1,2,4-triazol-1-yl）benzeneandmimb=1,2-bis（（2-methyl-1H-imidazole-1-yl）methy）benzene).Two examples of silver iodate compounds[pbmt]_0.5[AgI₂]1 and[H₂（mimb）]_0.5[Ag₂I₃]2 were synthesized from imidazol-1-yl)methyl)benzene and AgI under solvothermal conditions.The[pbmt]²⁺in 1 is obtained by in situ N-alkylation of dtb with methanol.1 is a 1-D chain structure,while 2 is a special three-dimensional open frame structure.Photoluminescence analysis showed that 1 emits yellow light at room temperature,and yellow and yellow-green light at different excitation wavelengths at low temperature,1 has fluorescent photo（thermo）chromic properties,while 2 does not have these properties.The fourth chapter selects 4 azole molecules（mimb=1,2-bis（（2-methyl-1H-imidazol-1-yl）methyl）benzene,1,3-bimb=1,3-bis（（2-methyl-1H-imidazol-1-yl）methyl）benzene,1,2-bimb=1,2-bis（（1H--imidazol-1-yl）methyl）benzene,dtb=1,4-Bis（1H-1,2,4-triazol-1-yl）benzene）,solvothermally reacted with PbI₂ and HI in different alcoholic solvents to form 4 new hybrid lead iodide compounds[H₂（mimb）][Pb₂I₆]3,[pmbmi][Pb₂I₆]4,[N,N-pmbmi][Pb₂I₆]5,[pbmt][Pb₂I₆]6.The[pmbmi]²⁺,[N,N-pmbmi]²⁺and[pbmt]²⁺in compounds 4-6 were obtained by in situ N-alkylation of organic bases with methanol.Optical properties show that 3-5 emit yellow or red light at low temperature and no light at room temperature.And through the exploration of photocatalytic performance,it was found that 3 has excellent photocatalytic performance.The fifth chapter utilizes two organic ligands(dtb=1,4-bis（1H-1,2,4-triazol-1-yl）benzene,dip=3,5-bis（1H-imidazol-1-yl）pyridine Three examples of copper iodate compounds with different structures[pbmt]_0.5[Cu I₂]7,[peti][Cu I₂]I.H₂O 8,[dip（Cu₃I₃）]9.Among them,[pbmt]²⁺is obtained by in situ N-methylation of dtb and methanol,and[peti]²⁺is obtained by in situ N-ethylation of dtb and methanol.The luminescence properties show that 9 emits orange light at room temperature and red light at low temperature,that is,9 has fluorescence thermochromic properties.更多还原