由无机建筑块构筑的具有隧道或螺旋链的三维开放骨架结构化合物的合成与表征

【作者】 段丽颖；

【导师】 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2004， 硕士

【摘要】 本文利用水热合成技术，通过调节反应条件和反应原料以及PH值合成了四种未见文献报道的具有隧道或螺旋链的三维开放骨架结构化合物：[C2N2H10]{(VO)(VO2)[V(OH2)](PO3.5)4}·H2O (1) (C3N2H12)4{CdMo12O24(HPO4)4(PO4)4(OH)6[Cd(H2O)]2}·4H2O (2) [La(pydc)2(H2O)][La(pydc)(H2O)2]·H2O (3) [Sm(pydc)2(H2O)][Sm(pydc) (H2O)2]·H2O (4)。通过对这四种化合物的晶体结构的讨论，初步探索了影响它们结构的因素，并研究了化合物2的电学性质。化合物(1)基本结构单元是由共边相连的钒三聚体{V3O16}被四个{PO4}四面体所固定形成的{V3P4O18}建筑块。{V3P4O18}建筑块通过共角相连形成新颖的三维开放骨架，无机骨架显示10元环交替排列的网络，并且沿a轴方向形成了新奇的一维隧道。无机骨架和客体分子间存在着强的氢键相互作用。化合物(2)代表了一类新奇的磷钼酸盐，{Mo6P4}单元被六配位的Cd(1)连接形成二聚体[Cd{Mo6P4}2]，该二聚体再通过Cd(2)连接形成新颖的三维开放骨架。并且首次采用碳糊电极法研究水热合成化合物的电化学性质。化合物(3)和(4) 是属于同构的化合物。化合物(3)包括两种基本结构单元，由配体pydc上μ3-O桥连起来的镧双核单元和1-D(O-La-O)n螺旋链。La(2)和La(2A)由不同配体pydc提供的两个μ3-O连接形成一个中心对称的二聚体。La(1)由羧基上的不同氧原子桥连形成围绕21螺旋轴 (O-La-O)n 一维螺旋链。配体pydc螯合配位于La(1) 原子并且平均分布在21螺旋轴两侧。一维螺旋链上相邻的La(1)沿着相反方向连接双核单元形成Z字形的层。层之间通过配体的羧基连接形成三维骨架。同时，在本文中还通过元素分析、红外光谱、光电子能谱和热重分析等手段对上述六种化合物进行了表征。更多还原

【Abstract】 In this paper, four novel 3-D open framework compound with tunnels or helical chains: [C2N2H10]{(VO)(VO2)[V(OH2)](PO3.5)4}·H2O (1) (C3N2H12)4{CdMo12O24(HPO4)4(PO4)4(OH)6[Cd(H2O)]2}·4H2O (2) [La(pydc)2(H2O)][La(pydc)(H2O)2]·H2O (3) [Sm(pydc)2(H2O)][Sm(pydc) (H2O)2]·H2O (4) have been hydrothermally synthesized through modifying synthetic conditions, starting materials and PH value. Structures of the six complexes have been determined by X-ray single crystal diffraction, and the influencing factors on structures have been discussed. The basic structural unit of compound (1) is {V3P4O18} building block, which is made up of tri-polymeric {V3O16} by edge-sharing fixed by four {PO4} tetrahedra. {V3P4O18} building blocks form novel 3-D open framework by corner-sharing, inorganic framework shows interesting 10-member rings network and forms novel 1-D tunnels along a axis. There are strong hydrogen bonding interactions between inorganic and guest molecules. Compound (2) represent a kind of novel molybdenum phosphate, {Mo6P4} units are linked by six-coordinated Cd(1) forming polymer[Cd{Mo6P4}2], which are connected by Cd(2) forming novel 3-D open framework with intersecting tunnels. Furthermore, bulk-modified carbon paste electrode is first used to study the electrochemical properties of hydrothermally synthesized compound. Compound (3) and (4) are isostructural compounds containing lanthanide binuclear dimer and 1-D lanthanide helical chain. La(2) and La(2A) are connected by two μ3-O of different pydc to form a central symmetrical dimer. La(1) were connected by the different oxygen atom of carboxyl and form a helical-shaped (O-La-O)n chain along 21 helical axes. The pydc ligands chelate coordinated to La(1) distributes around 21 helical axes. The adjacent La(1) on the chain connect lanthanide binuclear polymer with opposite direction. Z-shaped layer are connected <WP=5>by carboxyl of pydc to form a 3-D framework. Other characterizations for these six complexes by elemental analysis, IR, ESR, XPS, and thermal analysis have also been described.更多还原