新型多金属氧簇分子基化合物的合成、表征及性质研究

【作者】 李阳光；

【导师】 王恩波；

【作者基本信息】 东北师范大学 ， 无机化学， 2003， 博士

【摘要】 本论文利用已知的或新型的金属氧簇（包括多金属氧酸盐和3d过渡金属簇）为基本构筑单元，通过各种有机含N和含O配体的“剪切”、“修饰”或“桥连”，构筑新型多维的多金属氧簇分子基化合物，研究这类杂化材料的合成条件及规律，以及新物质结构和性能间的关系。 利用水热技术和有机溶剂合成方法，合成了20种新型的有机-无机杂化化合物，通过元素分析，IR，UV-vis，EPR，XPS，XRPD，TG-DTA和单晶X-射线衍射对晶体结构进行了表征，对化合物的热稳定性、光敏特性和磁学特性进行了初步研究。 1．通过引入{M_xL_y}（M=过渡金属离子，L=含N螯合配体）片段，水热合成和结构表征了8种新型的有机-无机杂化钒酸盐： [Ni（1,10’-phen）₃]₂[V₁₀O₂₆]（1） [M（2,2’-bipy）₃]₃[V₁₅O₃₆Cl]·3H₂O（M=Zn（2）, Co（3）, Fe（4）） [V^Ⅴ₄4O₁₀（1,10’-phen）]（5） [{Cu（2,2’-bipy）}₂V^Ⅳ₂V^Ⅴ₆O₂₁]（6） [Cu（1,10’-phen）]₂[V^ⅣV^Ⅴ₄As^Ⅴ₂O₁₉]·0.5H₂O（7） [H₂N（C₂H₄）₂NH₂]₄（H₃O）[PMoV₂Mo^Ⅵ₆V^Ⅳ₄O₄₀（V^ⅣO）₂)·H₂O（8） 化合物（1）～（4）是具有分立结构的笼型混价钒氧簇，发现使用具有不同空间占有率的螯合配体，对笼型钒氧簇的自组装有显著影响；化合物（5）是具有1-D梯子形链状结构的钒酸盐，螯合配体直接配位生长在这一无机物的骨架上；化合物（6）显示出一种2-D的层状钒酸盐网络，具有4-，5-，6-三种圆环；{Cu（2,2’-bipy）}片段配位生长在钒酸盐网络上；化合物（7）代表第一种由{M_xL_y}片段修饰的2-D砷钒氧酸盐网络。化合物（8）显示出一种高度还原的钼钒氧化物层交替排列的多阴离子。 2．利用多金属氧酸盐和冠醚为基本建筑单元，在有机溶剂中自组装形成7种新型多酸-冠醚杂化化合物，并进行了晶体结构表征和光致变色性质研究： [（DB18C6）Na（H₂O）_1.5]₂Mo₆O₁₉·CH₃CN（9） ［｛N3（DB18C6）（HZO）2｝3（HZO）21XMOIZO40’6DMF·CH3CN （X＝（10）人S（11）） ［｛NS（DB18C6）（DM）2｝2｛Na（DM）6｝21SIMO12O40（12） ［｛Na（DB18C）（HZO）2｝3］HSIMO12O40CH3CN（13） ［（DB18C6）（CH3OH）Na］ZW6O19·DB18C6·HZO（14） ［（DB18C6）（DMF）ZNedZW10O32’ZDMF·ZHZO（15） 化合物（）显示出一种由多阴离子和冠醚构筑的三维超分子网络，并具有10的沙漏型隧道；化合物＊0)和＊1)具有由冠醚构筑的2－D蜂巢型网络，多阴离子做为客体处于空穴中；化合物＊3)显示出一种由冠醚构筑的圆筒型通道：化合物＊4)和05)是由同多钨酸盐阴离子跟冠醚构筑的有机－无机杂化化合物。 发现化合物＊0卜＊杆＊5)具有显著的光致变色现象。3．利用3d过渡金属离子或由其构成的多核金属簇为构筑单元，将l，2人5－均苯四甲酸Otec)和螫合配体混合使用，借助水热合成技术合成并表征了5种新型的有机－无机配位聚合物，并进行了磁学性质研究：。 ［CC（2，2’七iPyZ（bteC）］n（16） ［Ni。（11’－phen）。（H。O）。（bte）］n（17） ［Niz（2，2’七中y）z（OH）z（HZbtec）］sn（18） 【CO4（2，丁七1P刃4（氏0）2（bteC川n（19） ［CO3（btC）（CZO4）（H2O）2n（2） 化合物O6）具有一种1－D的梯子型链状结构；化合物O7）显示出2－D的带有菱形格子状的网络结构；化合物＊8）是一种双核配位聚合物，具有10链状的构型，相邻的链通过OH基团和COOH基团的氢键作用连接成2－D超分子网络；化合物＊9)显示出一种具有手性结构特征的2＊配位聚合物网络，并且根据Flack参数N。52伴断，该化合物为孪晶，由 50％左旋和 50％右旋的结构组成。化合物p0)的基本单元为一三核钻金属簇，通过 btec和＊／’配体的连接，构筑成一种有趣的2－D互穿型网络结构，并通过btec配体的梭基基团将相邻的20网络连接成具有3－D的框架结构。 磁学性质研究发现，化合物＊7)、＊9)和（2）具有反铁磁性，而化合物08)具有铁磁性。更多还原

【Abstract】 The aim of this thesis is the synthesis of new molecular-based compounds with multi-dimensional structures on the basis of metal-oxo clusters (including polyoxometalates (POMs) and multi-nuclear 3d transition metal clusters), which are "passivated", "decorated" or "bridged" by various organic N-donor and/or O-donor ligands. The study on synthetic conditions and rules for these hybrid compounds and the exploration of relationships between structures and properties for these materials are also carried out.Twenty new organic-inorganic hybrid compounds have been synthesized on the basis of hydrothermal technique and/or organic solvent synthesis methods and structurally characterized by elemental analyses, IR, UV-vis, EPR, XPS, XRPD, TG-DTA and single crystal X-ray diffractions. The thermal stabilities, photochromic properties and magnetic properties of these compounds have been studied.1. Eight new organic-inorganic polyoxovanadates have been hydrothermally synthesized by the introduction of {MxLy} (M = transition metal ions, L = N-donor chelate ligands) fragments and structurally characterized:Compounds (1)-(4) exhibit mixed-valent and discrete cagelike polyoxovanadates. It is found that the use of chelate ligands with different steric possession may influence the self-assembly of oxovandates. Compound (5) possesses a novel 1-D ladderlike oxovanadate chain withphen groups directly coordinated on metal oxide skeletons. Compound (6) shows a novel 2-D oxovanadate layer with 4-, 5-, 6-net; the {Cu(2,2’-bipy)} fragments are coordinated directly on the inorganic network. Compound (7) represents the first 2-D arsenic oxovanadate framework decorated by {MxLy} fragments. Compound (8) exhibits a highly reduced polyoxoanion with phosphorus-centered alternate layers of Mo/V oxides.2. Seven new polyoxometalate-crown ether hybrid compounds have been synthesized in the organic solvent by virtue of polyoxoanions and crown ether building blocks. The photochromic properties have been studied:Compound (9) exhibits a new 3-D supramolecular framework with 1-D sandglass-like channels. Compound (10) and (11) possess the 2-D honeycomb-like network constructed from crown ether building blocks; polyoxoanions are encapsulated in cavities. Compound (13) shows a novel circle channels built from the crown ether building blocks. Compounds (14) and (15) are composed of isopolytungstates and crown ether moieties. It was found that compounds (10) # (11) and (15) possess the photochromic behaviors.3. Five new organic-inorganic coordination polymers have been hydrothermally synthesized on the basis of 3d transition metal ions or their multi-nuclear clusters connected by 1,2,4,5-benzenetetracarboxylate (btec) and chelate ligands. Their magnetic properties have been studied:Compound (16) exhibits a 1-D ladderlike chain. Compound (17) possesses an interesting 2-D rhombus-grid-like network. Compound (18) consists of dinuclear Ni clusters, which are linked by btec ligands to form a 1-D chain. The adjacent chains are linked into a 2-D wavelike layer via the strong OH@O hydrogen bonding interactions. Compound (19) possesses a chiral 2-D network. According the Flack parameter (0.52), the compound is an inversion twin crystal, containing 50% left-handed and 50% right-handed structures. Compound (20) contains a basic unit of trinuclear Co clusters, which are connected together by btec and C2O42- ligands and form an interesting 2-D interpenetrating network. The adjacent layers are linked into 3-D frameworks via btec ligands.It is found that compounds (17), (19) and (20) exhibit the antiferromagnetic interactions, while compound (18) shows the ferromagnetic interactions.更多还原