【作者】 刘海燕；

【导师】 马建方；

【作者基本信息】 东北师范大学 ， 无机化学， 2011， 博士

【摘要】 本论文旨在利用过渡金属离子、不同类型的柔性含氮多齿配体和多钼酸盐阴离子,在水热条件下,构筑一系列新颖的多金属氧酸盐基的无机-有机杂化材料。研究这类化合物的合成条件,分析其网络所属的拓扑类型,考察过渡金属离子、有机配体结构和反应的pH值对化合物结构的影响,探究新物质结构与性能之间的关系,为新型多钼酸盐功能材料的定向合成提供理论和实验基础。在实验中我们利用柔性的2,4,6-三甲基-1,3,5-(三亚甲基苯)三(1,2,4-三氮唑)(ttb)和一系列双吡啶基苯并咪唑类化合物作为修饰配体,过渡金属离子和(NH)4Mo7O24·4H2O为无机组分,在水热条件下合成了23种未见文献报道的基于多钼酸盐的无机-有机杂化化合物。通过元素分析、IR、XPRD、XPS、TGA和X-射线单晶衍射分析对这些化合物的结构进行了表征,并对部分化合物进行了电化学、荧光和光催化性质的初步研究。1.利用柔性的ttb有机配体和不同的过渡金属离子设计合成了6种新颖的基于{Mo8}阴离子簇的无机-有机杂化化合物。[CuⅡ2(ttb)2(β-Mo8O26)(H2O)2]·2H2O(1)CuⅠ4(ttb)2(β-Mo8O26)(H2O)(2)[CuⅠ4(ttb)3(β-Mo8O26)](3)[Ni2(ttb)2(β-Mo8O26)(H2O)6]·2 H2O(4)[Zn2(ttb)2(α-Mo8O26)(H2O)2](5)[AgⅠ4(ttb)2(β-Mo8O26)](6)化合物1-6分别具有2D或3D的网络结构,尤其是化合物1-3还呈现了两重互穿的缠结结构。这些化合物结构的多样性表明,多齿的ttb有机配体、过渡金属离子电子构型和八钼酸盐的配位模式对这些化合物的最终结构产生重要的影响。2.利用不同类型的1,1’-(1,3-丙基)二[2-(2-吡啶基)苯并咪唑](opr)、1,1’-(1,4-丁基)二[2-(2-吡啶基)苯并咪唑](obu)、1,1’-(1,5-戊基)二[2-(2-吡啶基)苯并咪唑](ope)和1,1’-(1,4-丁基)二[2-(3-吡啶基)苯并咪唑](mbu)柔性配体和过渡金属离子合成了8种基于八钼酸盐的无机-有机杂化化合物。[CuⅠ4(opr)2(β-Mo8O26)]·2 H2O(7)[CuⅡ4(ope)8(δ-Mo8O26)2]·4 H2O(8)[CuⅡ2(obu)2(β-Mo8O26)]·2 CH3OH·H2O(9)[Zn2(obu)2(β-Mo8O26)(H2O)2]·2 H2O(10)[Co2(obu)3(β-Mo8O26)]·3H2O(11)[Ni2(obu)3(β-Mo8O26)]·3H2O(12)[CuⅠ(mbu)2(β-Mo8O26)(H2O)2]·4 H2O(13)[Ag4(mbu)2 (γ-Mo8O26)](14)化合物7-12分别具有1D和2D的低维结构,化合物13和14表现为3D和2D的网络结构,这个结果可能是由于有机配体的不同的结构引起的。在化合物7-12中具有螯合基团的柔性配体(opr、ope和obu),由于螯合作用占据了过渡金属离子的配位点,阻碍了多酸阴离子与金属离子的配位,从而很难得到高维的网络结构。3.利用柔性的1,1’-(1,4-丁基)二[2-(4-吡啶基)苯并咪唑](pbu)配体,通过调节反应体系不同的pH范围,得到了4种新颖的从1D到3D不同结构的八钼酸盐基无机-有机杂化化合物。(H4pbu) (γ-Mo8O26)·2H2O(15) [Cu(H2pbu)(β-Mo8O26)(H2O)2]·3H2O(16) [Cu(H2pbu)(γ-Mo8O26)]·3H2O(17) [Cu(Hpbu)2(β-Mo8O26)](18)在pH≈1时,化合物15具有1D的无机钼氧链结构。当升高pH值为2.5时,合成了化合物16和17,它们分别具有2D和3D的框架结构。然而在pH≈3.5时,我们得到了1D结构的化合物18。这些结果表明,反应体系的pH值影响多酸基无机-有机杂化材料的自组装过程。4.利用不同结构的1,1’-(1,3-丙基)二[2-(4-吡啶基)苯并咪唑](ppr)、1,1’-(1,5-戊基)二[2-(4-吡啶基)苯并咪唑](ppe)和mbu配体,成功的组装了3个新颖的两种不同构型多钼酸盐共存的杂化化合物。[Ag8(ppr)4(α-Mo8O26)(β-Mo8O26)(H2O)3]·H2O(19) CuⅠ3.1CuⅡ0.5(β-Mo8026)0.5(ζ-Mo7ⅥMoⅤO26)0.5(mbu)2(H0.8mbu)0.5(20) [Cu(H2ppe)2(γ-Mo8O26)] (Mo6O19)·2H2O(21)化合物19和20中,分别包含了两种不同构型的钼八异构体在同一晶体中,而化合物21中同时包含了铝六和钼八两种多阴离子簇。这些化合物的成功获得,说明可以通过合理的调节反应条件,来控制多酸基杂化化合物的组装过程,从而得到两种或多种不同类型多酸共存的无机-有机杂化材料。5.在水热条件下,采用原位合成的方法,以有机胺为模板剂,在过渡金属离子的参与下,得到了2种新型的低核钼氧簇化合物。[(H2ttb)2(ttb)2(Cd2Mo20O64)(H2O)2]·4H2O(22) [CuⅡ4(opr)2(Mo12O40)]·3H2O(23)化合物22晶体结构中包含了一个新型的夹心型杂多二十钼酸盐簇{Mo20Cd2}。在化合物23中,新型的{Mo12}同多钼氧簇通过彼此共边相连接形成了一维无限的无机钼氧链结构。化合物22和23的成功获得,进一步地丰富了多钼酸盐的合成化学和结构化学。更多还原

【Abstract】 In this paper, a new series of organic-inorganic hybrid materials based on polymolybdates, transition metal ions and flexible multidentate N-containing ligands have been synthesized under hydrothermal conditions. The influence of the reaction conditions for the final products was investigated such as structure of the organic ligand, metal cations, and pH value. The study on synthetic conditions for these new compounds, topological analyses, and the exploration of relationships between structures and properties for these new materials are also carried out.Twenty-three new organic-inorganic hybrid compounds based on polymolybdates and transition metal ions have been successfully obtained by utilizing 1,3,5-tris(1,2,4-triazol-l-ylmethyl)-2,4,6-trimethyl benzene (ttb) and bis-[(pyridyl)-benzimidazole] ligands. Their structures have been determined by single crystal X-ray diffraction analyses, IR, XPRD, XPS, TGA and elemental analyses, In addition, the luminescent, electrochemical, and photocatalytic properties of some complexes have also been studied.1. Six organic-inorganic hybrid compounds based on octamolybdate building blocks and metal-organic fragments with flexible ttb ligand have been synthesized. [CuⅡ2(ttb)2(β-Mo8O26)(H2O)2]-2H2O (1) CuⅠ4(ttb)2(β-Mo8O26)(H2O) (2) [CuⅠ4(ttb)3(β-Mo8O26)3 (3) [Ni2(ttb)2(β-Mo8O26)(H2O)6]-2H2O (4) [Zn2(ttb)2(α-Mo8O26)(H2O)2] (5) [Ag4(ttb)2(β-Mo8O26)] (6)These complexes display fascinating 2D and 3D frameworks. Furthermore, compounds 1-3 exhibit 2-fold interpenetrating frameworks, respectively. The structural diversities of the complexes show that the ttb ligand, the electronic configuration of metal ion, and the coordination mode of the octamolybdate anion play important roles in the formation of the hybrid compounds.2. Eight octamolybdate-based hybrid compounds based on flexible opr, ope, obu, and mbu ligands{opr=1,1’-(1,3-propanediyl)bis[2-(2-pyridyl)benzimidazole], opr= 1,1’-(1,5-pentanediyl)bis[2-(2-pyridyl)benzimidazole], obu= 1,1’-(1,4-butanediyl)bis[2-(2-pyridyl)benzimidazole], and mbu= 1,1’-(1,4-butanediyl)bis[2-(3-pyridyl)benzimidazole]} have been designed and syntheszed. [CuⅠ4(opr)2(β-Mo8O26)]·2H2O (7) [CuⅡ4(ope)8(δ-Mo8O26)2]·4H2O (8) [CuⅡ2(obu)2(β-Mo8O26)]·2CH3OH·H2O (9) [Zn2(obu)2(β-Mo8O26)(H2O)2]·2H2O (10) [Co2(obu)3(β-Mo8O26)]·3H2O (11) [Ni2(obu)3(β-MogO26)]·3H2O (12) )2]-4H2O (13) [Ag4(mbu)2 (y-Mo8O26)] (14)Compounds 7-12 show 1D and 2D structures, respectively, while compounds 13 and 14 exhibit 3D and 2D frameworks, respectively. This result may be attributed to the different structure of the organic ligand. From the structures of the compounds 7-12, it can be seen that the coordination sites of the metal ions are occupied by the chelating group of the flexible ligands, and the polyanions bonded to metal ions is hindered. Thus, it is difficult to form high dimensional structures using chelating ligands.3. Four octamolybdate hybrid materials based on a flexible 1,1’-(1,4-butanediyl)bis[2-(4-pyridyl)benzimidazole] (pbu) ligand have been synthesized at different pH values under hydrothermal conditions. (H4pbu)(γ-Mo8O26)·2H2O (15) [Cu(H2pbu)(β-Mo8O26)(H2O)2]·3H2O (16) [Cu(H2pbu)(γ-Mo8O26)]·3H2O (17) [Cu(Hpbu)2(β-Mo8O26)] (18) Compound 15, which is hydrothermally prepared at pH≈1, exhibits a rare 1D molybdenum oxide chain. Compounds 16 and 17 are hydrothermally obtained at pH≈2.5. They show 2D and 3D frameworks, respectively. However, at pH≈3.5, the 1D chain structure of 18 is obtained. From the syntheses of these compounds, it can be seen that the pH value of the reaction system plays a crucial role in the assembly of polyoxometalate-based (POM) metal-organic frameworks.4. Three novel compounds coexisting different forms of polymolybdate have been successfully synthesized by using 1,1’-(1,3-propanediyl)bis[2-(4-pyridyl)benzimidazole] (ppr),1,1’-(1,5-pentanediyl)bis[2-(4-pyridyl)benzimidazole] (ppe), and mbu ligands. [Ag8(ppr)4(α-Mo8O26)(β-Mo8O26)(H2O)3]·H2O (19) CuⅠ3.1CuⅡ0.5(β-Mo8O26)0.5(ζ-Mo7ⅥMoⅤO26)0.5(mbu)2(H0.8mbu)0.5 (20) [Cu(H2ppe)2(γ-Mo8O26)]·(Mo6O19)·2H2O (21)Compounds 19 and 20 contain two kinds of (Mo8O26)4- isomers in the same crystal architecture, respectively. However, compound 21 is a rare example coexisting two kinds of (γ-Mo8O26)4- and (MO6O19)2- anion clusters. This result suggests that by rational reaction condition, assembly of POM-based coordination polymers may be controllable, so that a crystal structure of the coexistence two or more kinds of POMs can form.5. Two new low-nuclear polymolybdate clusters were successfully isolated by the introduction of flexible multidentate ligands and transition metal ions.[(H2ttb)2(ttb)2(Cd2Mo2oO64)(H20)2]·4H20 (22)[CuⅡ4(opr)2(Mo12O40)]·3H2O (23)Compound 22 contains a new "sandwich type" heteropolymolybdate clusters{Mo20Cd2}. In 23, the{Mo12} clucters are linked together through shared edges to form a 1D molybdenum oxide chain. Their successful isolation further riches the synthetic chemistry and structural chemistry of the polymolybdates.更多还原