超分子材料是基于分子间的相互作用力进行自组装成复杂的、有序的聚集体，而配位化合物超分子材料作为一种新型的功能性晶体材料，它具有常规材料无法比拟的优势。配合物的结构决定其性能，设计合成拥有特殊结构和预期性能的功能性配合物一直是科研人员极为焦距的研究方向。之所以含氮杂环和含氮杂环羧酸这类的有机配体一直是化学、材料学等学科中研究的热点，是因为这类有机配体的种类繁多，氮／氧原子的配位能力强，配位模式多样化，可以与多种金属原子或离子进行定向设计出独特结构的配位化合物材料，并且多氮类的有机配体本身就自带多种性能，金属配合物更有利于在光学、磁学、半导体材料等方面进行研究应用。 基于上述考虑，本论文设计了氮杂环类及氮杂环羧酸类的有机配体采用水热溶剂法和扩散法合成得到一系列的金属配合物，通过红外光谱、X-单晶衍射、元素分析、质谱、核磁等方法确定其结构，通过固态荧光光谱、固态紫外漫反射光谱、热重及差热分析、磁化率等方面研究了其光学、磁学、吸附、半导体材料等物理性能，并通过时间密度泛函理论计算(TDDFT)研究了其电荷转移及能量传递的相关机理，以期待获得性能优良的超分子材料。具体研究内容如下： (1)以3-羟基-2-甲基喹啉-4-羧酸(HMCA)为主要配位，利用不同的稀土金属与过渡金属配位方式，合成出了一系列的新型金属-喹啉羧酸[PrCl(H₂O)₃(L)(HL)]〓nCl(1)、[Zn(CH₃PH)₄(L)₂](2)、[Ni(L)₂(EtOH)₂(MeOH)₂](3)、 [Cu(L)(Phen)(H₂O)](CH₃OH)(4)(HL=3-羟基-2-甲基喹啉-4-羧酸和Phen= 1，10-邻菲哕啉)超分子化合物。晶体结构表明：化合物(1)为单斜P2(1)空间群2-D维链结构；化合物(2)为三斜P1空间群0-D结构；配合物(3)为三斜P-1空间群1-D结构；配合物(4)为单斜P2(1)／c空间群0-D结构。光致发光表明：化合物(1)～(4)分别为潜在的红光，蓝光，绿光，及蓝紫色光致发射材料。固态漫反射光谱表明配合物(1)～(4)分别具有2.75eV，1.73eV，2.25eV，1.91eV的宽光学带隙，四种超分子化合物都是良好的宽光学带隙半导体材料的候选物。 TDDFT计算研究表明了(2)～(4)的电荷转移分别为LMCT，LLCT，LLCT。 (2)利用异烟酸、HgCl₂、稀土(EuCl₃·6H₂O和TbCl₃·6H₂O)通过水热法得到两种新型稀土汞[Ln(IA)₃(H₂O)₂]n(Hg₃Cl₉)n·4nH₂O(Ln=Eu(5)和Tb(6)；IA=异烟酸)超分子化合物。晶体结构表明：两者化合物均为三斜PĪ空间群3-D维链结构；固态漫反射光谱表明：化合物(5)(6)分别具有2.81eV,3.47eV的宽光学带隙，两者均是良好的宽光学有机半导体材料的候选物；光致发光光谱表明： (5)(6)分别为潜在的红光、绿光光致发射材料，通过能量转移机理进一步说明其发光特性。 (3)利用12族／15族金属和2，2’-联吡啶、4，4’-联吡啶的体系通过原位反应得到了三种新型的原位反应[(N，N’-dimethyl-2，2’-bipy)₂(Bi₂Cl₁₀)·2H₂O(7)， α-CuCl₄(N，N’-dimethyl-2，2’-H₂bipy)(8)，β-CuCl₄(N，N’-dimethyl-2，2’-H₂bipy)(9)超分子。晶体结构表明：化合物(7)～(9)分别为单斜P2₁／n空间群3-D维链结构；单斜C2／c空间群2-D维链结构；正交Fdd2空间群3-D维链结构。光致发光光谱表明：(7)～(9)为潜在的绿光光致发光材料。TDDFT计算研究表明了(7)～(9)的电荷转移均为LLCT。 (4)利用TCPP(四-(4羧基苯基)卟啉)、T(4’-OMePh)P([四-(4-甲氧基苯基)卟啉)、TPPS(四-(4-磺基苯基)卟啉)和稀土元素得到了一系列镧系卟啉[Ln〓(TPPS〓)]〓·nH₅O₂(Ln=La(10)，Sm(11)，Eu(12)；TPPS=tetra(4sulfonatophenyl)porphyrin)超分子，利用溶剂热技术和5，10，15，20-4-(4-(三唑-1-基)苯基)的溶剂热技术设计并合成了新的含IIB的金属锌卟啉超分子[Zn₂Cl₄ (5，10，15，20-tetra-(4-(triazol-1-y1)phenyl)porphyridine)]〓nCl·nH₃O·7nH₂O(13)。晶体结构表明：化合物(10)～(12)均为四方P4／mcc空间群3-D维链结构；配合物(13)为正交Pmmn空间群1-D维链结构。CO₂的吸附能力表明配合物(10) ～(12)分别为0.9 mmol／g，1.2 mmol／g，1.9mmol／g，均为良好的CO₂的吸附性能。磁学性能研究表明：化合物(10)～(12)分别为良好的潜在铁磁性，反铁磁性材料，顺铁磁性材料。固态漫反射光谱表明化合物(13)的光学带隙为1.60eV，具有良好的潜在半导体材料。光致发光性能研究表明化合物(13)为潜在的绿色光致发光材料，TDDFT计算研究表明了化合物(13)的光致发光是归因于π-π*电荷的转移。 (5)利用2,2’-biim、4,4’-bipy、2,2’-bi-1H-imidazole、4-吡啶-3-苯甲酸配体与IIB金属得到三种超分子[Zn₃(2，2’-bi-1H-imidazole)₂(1H-biimidazole)₂(SO₄)₂]〓(14)、 {[Cd(2，2’-biim)(4，4’-bipy)(H₂O)(ClO₄)](ClO₄)}〓(15)、[CdCl₂(C₁₃H₁₂NO₂)]〓(16) (C₁₃H₁₂NO₂=N-methyl-4-pynd-3-ylbenzoic acid)。晶体结构表明：化合物(14)～(16)分别为单斜C2／c空间群3-D维链结构；正交Pna2₁空间群3-D维链结构；单斜P2₁／c空间群1-D维链结构。光致发光性能光谱研究表明：化合物配合物(14) ～(16)分别具有潜在的蓝色光致发光；绿色光致发光材料；蓝色光致发光材料。 TDDFT计算研究表明：化合物(14)～(16)的发光本质均为LLCT。固态漫反射光谱研究表明：化合物(14)(15)的光学带隙分别为2.08eV，3.25eV，均为高效的光学带隙半导体的候选材料。 (6)利用吡嗪／氰吡啶作为N-供体配体之一与IIB族光致发光金属的Gd(II)和磁性活性金属中心Fe(III)原子得到两种新型二维层状结构的光致发光超分子[CdBr₂(C₄H₄N₂)]〓(17)、(C₆H₅N₂)(FeBr₄)(18)。晶体结构表明：化合物(17)为正交C222空间群2-D维链结构；化合物(18)为三斜PĪ空间群3-D维链结构。光致发光光谱研究表明：化合物(17)为潜在的绿光发射光谱材料；化合物(18)为潜在的紫光发射光谱材料。通过TDDFT的计算进行一步揭示配合物的发光机理，化合物(17)的电荷转移归因于MLCT和LLCT共同作用；化合物(18)的电荷转移归因于LMCT。 关键词：氮杂环；氮杂环羧酸；超分子材料：合成；性能；理论计算

 As a new type of functional crystal material, coordination compounds have incomparable advantages over conventional materials. Because the structure of complexes determines their properties, the design and synthesis of functional complexes with special structures and expected properties has always been of great interest to researchers. The reason why organic ligands such as nitrogen-containing heterocyclic and carboxylic acids have always been the focus of research in chemistry and materials science is that these organic ligands have many kinds, strong coordination ability of nitrogen/oxygen atoms and diverse coordination modes. They can be directionally designed with a variety of metal atoms or ions to coordinate compound materials with unique structures, and the organic ligands of polynitrogen have many properties. Metal complexes are more conductive to the research and application in optics, magnetic, semiconductor materials and so on. Based on the above considerations, a series of organic ligands of nitrogen heterocyclic and nitrogen heterocyclic carboxylic acids were designed and synthesized by hydrothermal solvent method and diffusion method. Their structures were determined by infrared spectroscopy, X-single crystal diffraction, elemental analysis, mass spectrometry, nuclear magnetic resonance. The properties of optical, magnetic, adsorptive and semiconductor were studied by solid-state fluorescence spectroscopy, solid-state ultraviolet diffuse reflectance spectroscopy, thermogravimetric and differential thermal analysis, and magnetic susceptibility. The mechanism of molecular energy transfer was studied by density functional theory (TDDFT). Specific research contents are as follows: (1)A series of novel metal-quinoline carboxylic acid complexes have been synthesized by solvothermal method using 3-hydroxy-2-methylquinoline-4-carboxylic (HMCA) as the main ligand and different coordination modes between rare earth metals and transition metals. [PrCl(H₂O)₃(L)(HL)]〓nCl(l) 、[Zn(CH₃PH)₄(L)₂](2)、[Ni(L)₂(EtOH)₂(MeOH)₂](3)、[Cu(L)(Phen)(CH₃OH)] (H₂O) (4)The structures were characterized by infrared spectroscopy, mass spectrometry, nuclear magnetic resonance, elemental analysis and single drystal structure. The properties were studied on photoluminescence and semiconductor, the energy transfer mechanism was studied by the time dependent density functional theory(TDDFT). Four different crystal structures were obtained: complex (1) is monoclinic P2(1) space group 2-D chain structure; complex (2) is triclinic P1 space group 0-D structure; complex (3) is triclinic P-1 space group 1-D structure; complex (4) is monoclinic P2(1)/C space group 0-D structure. The photoluminescence spectra show that the complexes (1) are potential red photoemission materials; the complexes (2) are potential blue photoemission materials; the complexes (3) are potential green photoemission materials; and the complexes (4) are potential blue-purple photoemission materials. Solid-state diffuse reflectance spectra show that complex (1) has a wide optical band gap of 2.75 eV; complex (2) has a wide optical band gap of 1.73 eV; complex (3) has a wide optical band gap of 2.25 eV; complex (4) has a wide optical band gap of 1.91 eV. All four complexes are good candidates for wide optical band gap semiconductor materials. TDDFT show that charge transfer of complex (2) is LMCT; charge transfer of complexes (3) is LLCT; and charge transfer of complex (4)is LLCT. (2)Two new rare earth mercury complexes [Ln(IA)₃(H₂O)₂]n(Hg₃Cl₉)n·4nH₂O (Ln=Eu(5) and Tb(6); IA=isonicotic acid) were synthesized by hydrothermal method using isonicotic acid, HgCl₂, EUCl₃·6H₂O and TbCl₃·6H₂O. Their properties and structures were characterized by photoluminescence, semiconductor, energy transfer mechanism, elemental analysis and single crystal X-ray diffraction. Crystal structure shows that both complexes are 3-D chains of triclinic PĪ space group; solid-state diffuse reflectance spectra show that complex (5) has 2.81 eV wide optical band gap; complex (6) has 3.47 eV wide optical band gap, both of which are good candidates for wide optical organic semiconductor materials. The photoluminescence spectra show that the complexes (5) (6) are potential red and green photoluminescent materials, and their luminescent properties are further explained by energy transfer mechanism. (3)Three novel in-situ complexes [(N,N’-dimethyl-2,2’-bipy)₂(Bi₂Cl₁₀)-2H₂O (7), α-CuC14(N,N′-dimethyl-2,2′-H2bipy) (8), β-CuC14(N,N′-dimethyl-2,2′-H2bipy) (9) were obtained by in-situ reaction of 12/15 metal and 2,2’-bipyridine systems. The structures were characterized by IR, elemental analysis and single crystal X-ray diffraction. The photoluminescence properties, semiconductor properties and energy transfer mechanism were studied. Crystal structure shows that complex (7) is a 3-D chain structure of monoclinic P2₁/n space group; complex (8) is a 2-D chain structure of monoclinic C2/c space group; complex (9) is a 3-D chain structure of orthogonal Fdd2 space group. Photoluminescence spectra show that complex (7)～(9) is a potential green photoluminescent material. TDDFT calculations show that charge transfer of complexes (7)～(9) is all (LLCT). (4)A series of lanthanide porphyrins, [Ln〓(TPPS)〓]〓nH₁O₂(Ln = La (10), Sm (11), Eu (12); H₂TPPS = tetra(4-sulfonatophenyl)porphyrin), have been synthesized through solvothermal reactions And also a new zinc porphyrin complex [Zn₂Cl₄(5,10,15,20-tetra-(4-(triazol-l-yl)phenyl)porphyridine)]〓nCl·nH₃O·7nH₂O (13) containing IIB has designed and synthesized by solvothermal technique using 5,10,15,20-tetra-(4-(triazol-l-yl)phenyl ligand. The structures were characterized by IR, elemental analysis and single crystal X-ray diffraction. Crystal structure shows that the complexes (10)～(12) are tetragonal P4/mcc space group 3-D chain structure, and the complexes (13) are orthogonal Pmmn space group 1-D chain structure. The adsorption capacity of CO₂ indicated that the complexes (10)～(12) were 0.9 mmol/g, 1.2 mmol/g and 1.9 mmol/g, respectively. All of them had good adsorption capacity for CO₂. The magnetic properties show that complex (10) is a good potential ferromagnetic material, complex (11) is a good potential antiferromagnetic material, and complex (12) is a good potential paraferromagnetic material. The solid-state diffuse reflectance spectra show that the optical band gap of complex (13) is 1.60 eV, which has good potential for semiconductor materials. Photoluminescence studies show that complex (13) is a potential green photoluminescent material. TDDFT show that the photoluminescence of complex (13) is attributed to the charge transfer of π-π*. (5)A series of novel three complexes [Zn₃(2,2′-bi-lH-imidazole)₂ (1H-biimidazole)₂(SO₄)₂]〓(14)、{[Cd(2,2′-biim) (4,4′-bipy)(H₂O)(ClO₄)](ClO₄)}〓 (15)、[CdCl₂(C₁₃H₁₂NO₂)]〓(16) (C₁₃H₁₂NO₂ = N-methyl-4-pyrid-3- ylbenzoic acid) have been synthesized through solvothermal reactions using 2,2′-biim, 4,4′-bipy, 2,2′-bi-1H-imidazole、4-pyridyl-3-benzoic acid ligand and IIB metal. The structures were characterized by infrared spectroscopy, mass spectrometry, nuclear magnetic resonance, elemental analysis and single drystal structure. The crystal structure shows that the complex (14) is a monoclinic C2/c space group 3-D chain structure; the complex (15) is an orthogonal Pna2₁ space group 3-D chain structure; and the complex (16) is a monoclinic P2₁/c space group 1-D chain structure. Photoluminescence spectra show that complex (14) is a potential blue photoluminescent material, complex (15) is a potential green photoluminescent material, and complex (16) is a potential blue photoluminescent material. TDDFT show that the luminescent nature of complex (14)～(16) is LLCT. Solid-state diffuse reflectance spectroscopy shows that the optical band gaps of complex (14) (15) are 2.08eV and 3.25eV, respectively, and they are all candidate materials for high-efficiency optical bandgap semiconductors. (6)Two novel two-dimensional layered photoluminescent complexes [CdBr₂(C₄H₄N₂)]n (17), (C₆H₅N₂)(FeBr₄) (18) were synthesized by pyrazine or cyanopyridine as one of N-donor ligands and Gd(II) and Fe(III) atoms of IIB group. The complexes were characterized by infrared spectroscopy, mass spectrometry, nuclear magnetic resonance, elemental analysis and single drystal structure. The crystal structure shows that the complex (17) is a 2-D chain structure of the orthogonal C222 space group and the complex (18) is a 3-D chain structure of the triclinic PĪ space group. The photoluminescence spectra show that the complex (17) is a potential green light emission spectral material and the complex (18) is a potential purple light emission spectral material. TDDFT was used to reveal the luminescence mechanism of complexes. The charge transfer of the complex (17) is attributed to the interaction of MLCT and LLCT, and the charge transfer of the complex (18) is attributed to LMCT. Key Words: nitrogen heterocyclic and carboxylic acids; supramolecular materials; Preparation, properties; theoretical calculations