多金属氧酸盐作为构筑块自组装合成新型功能性分子材料

本文概述了以多金属氧酸盐为构筑块合成新型功能性分子材料的研究状况和新进展 ,对这类化合物在催化、导电性、磁性和LB膜等方面的应用前景作了评述和展望     

Organofunctional Metal Oxide Clusters as Building Blocks for Inorganic-Organic Hybrid Materials

The controlled hydrolysis of metal alkoxides in the presence of methacrylic acid results in metal oxide clusters capped by polymerizable methacrylate ligands. Radical polymerization of small portions of such clusters with organic co-monomers allows the preparation of an interesting new type of inorganic-organic hybrid polymers in which the metal oxo clusters efficiently crosslink the organic polymers chains. SAXS investigations revealed that the clusters may aggregate to form clusters of clusters. The properties of the hybrid materials, such as thermal stability, swelling, dielectric and mechanical properties, depend not only on the portion of incorporated cluster, i.e. the crosslinking density, but also on the kind of employed cluster.     

Towards Syntheses and Structures of Heterometallic Clusters Containing Tantalum-tetrachalcogenato Building Blocks

An approach to tackle the synthesis of mixed-transition metal tantalum chalcogenide clusters is described. The synthesis of 1/_∞[Li₃(TaSe₄)(MeCN)₄]_∞ (1) will in future allow the construction of Ta–Se-transition metal clusters. The potential of this route was demonstrated by the synthesis of the mixed-metal Ta–S–Fe and Ta–S–Cu complexes (Et₄N)₃[Fe₂(SPh)₄(TaS₄)] (2) and [Cu₃(TaS₄)(PPh₃)₄] (3). Dedicated to Professor Günter Schmid on the occasion of his 70th birthday.     

Syntheses, Structures, and Some Properties of Three Vanadium Selenites

Three novel vanadium selenites with the formulae [（VO2）（1,10-phenanthtoline）（SeO3H）]2 1, [（VO2）（2,2′-bipyridine）]2（SeO3） 2 and [（VO）（H2O）（SeO3）2]2（HaEDD） 3 （EDD = N1,N1′-（ethane-1,2-diyl）diethane-1,2-diamine） were hydrothermally synthesized, and characterized with elemental analysis, FT-IR spectrum, Raman spectrum, TG-DTA analysis, EPR spectra, and single-crystal X-ray diffraction analysis. Compound I belongs to the triclinic system, space group P1^- with a = 7.7527（5）, b = 9.5345（10）, c = 9.8192（8） A^°, α = 92.712（3）, β = 105.540（3）, γ = 108.154（4）°, V = 657.66（1） A^°^3, Mr = 782.22, Z = 1, F（000） = 384,μ（MoKa） = 3.544 mm^-1, R = 0.0432 and wR = 0.1142; Compound 2 is of orthorhombic system, space group F212121 with a = 7.6574（15）, b = 14.916（3）, c = 19.085（4） A, V = 2179.8（8） Aa, Mr = 605.21, Z = 4, F（000） = 1200, μ（MoKa） = 2.579 mm^-1, R = 0.0338 and wR = 0.0658; Compound 3 belongs to the triclinic system, space group P1^- with a = 9.247（2）, b = 9.659（2）, c = 7.2651（19） A^°, α = 98.171（7）, β = 103.709（5）, γ = 114.712（13）°, V = 550.9（2） A^°^3, Mr = 828.03, Z = 1, F（000） = 400, μ（MoKa） = 7.537 mm^-1, R = 0.0641 and wR = 0.2118. Compound 1 is constructed from alternating corner-shared [VO4N2] octahedra and SeO3H units, forming a dimeric vanadium unit. These assemblies are further linked into an infinite chain via hydrogen bonds along the a axis. In the structure of 2, two distinct V centers form centrosymmetric [V2O6N4] clusters through edge-sharing, and the SeO3 unit serves as a capping unit to fix the oxovanadate cluster. In the structure of 3, each [VO6] octahedron shares four oxygen atoms with adjacent Se atoms, while every SeO3 unit shares two oxygen atoms with neighboring V atoms. This connectivity of alternating VO6 and SeO3 units results in a joint-like chain. Based on the TGA analysis, these three compounds are thermally stable under 200℃ .     

Syntheses and Crystal Structures of Two New Macrocyclic Compounds

Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I > 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073 , the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I > 2σ(I).     

Spectrophotometric Determination of Vanadium in Complex Materials Using N-m-TMBHA and Thiocyanate

Abstract

Vanadium(V) reacts with N-m-Tolyl-p-methoxy benzohydroxamic acid to form 1:2 (metal to ligand) complex containing a basic V=O group and an acidic V-OH group, which forms addition compounds with thiocyanate to give a hyper and bathochromic effect in chloroform. On the basis of this bathochromic effect of thiocyanate a rapid, selective and sensitive method for the spectrophotometric determination of vanadium(V) has been developed. The blue coloured complex of vanadium(V) is extractable in chloroform having absorption maxima at 580nm and max 7100 ±50 1. mole^?1 cm^?1. The method is free from interferences of Mo(VI), W(VI), Zr(IV) and has been successfully applied for the analysis of steels and other complex materials.     

Cyclodextrins as Building Blocks for Supramolecular Structures and Functional Units

Cyclodextrins are frequently used as building blocks, because they can be linked both covalently and noncovalently with specificity. Thus one, two, three, seven, fourteen, eighteen, or twenty substituents have been linked to one β-cyclodextrin molecule in a regioselective manner. Furthermore, Cyclodextrins may serve as organic host molecules. Their internal cavity is able to accommodate one or two guest molecules. Conversely, suitable guest molecules can be used to thread one, two, or many (one hundred or more) cyclodextrin rings. The resulting supramolecular structures are often formed in solution, which allows characterization by high-resolution spectroscopic methods. Chemical conversion of these structures provides molecular architectures such as catenanes, rotaxanes, polyrotaxanes, and tubes, which are not readily prepared by other methods. The particular properties of Cyclodextrins can also be employed, for example, for the chromatographic separation of complex mixtures of substances, even racemates, by molecular recognition. Cyclodextrins and their derivatives have been found to be remarkably active catalysts as well. Finally, since Cyclodextrins can favorably influence the release of drugs, many new applications will certainly be developed in the near future.     

Polyoxometalates as Inorganic Building Blocks of Multifunctional Molecular Materials

The use of polyoxometalates (pOM's) as inorganic component in the synthesis of new molecular hybrid materials is presented. Here we show that the combination of organic molecules of the tetrathiafulvalene (TTF) type or perylene (per) with POM's yields new radical salts with unprecedented structures that present interesting magnetic and/or electrical properties or coexistence of both. The first true metallic radical salt containing a POM has been prepared and characterized. We also describe the recent results obtained by combining magnetic POM's with the organometallic cation decamethylferrocene.     

Linear Copper Complex Arrays as Versatile Molecular Strings: Syntheses,Structures, Luminescence,and Magnetism

The defined linear arrangement of metal atoms in discrete coordination complexes or polymers is still one of the most intriguing challenges in synthetic chemistry. These chain arrangements are of fundamental importance, because of their potential applications as molecular wires and single molecule magnets (SMM) in microelectronic devices on a molecular scale. Oligonuclear Group 11 metal complexes with suitable bridging ligands, specifically those that are based on copper as the first choice of a cheap precursor coinage metal, are of particular interest in this regard. This is due to the superior luminescence properties of these linear clusters that often show d¹⁰⋅⋅⋅d¹⁰ interactions in their molecular structures. The combination of Cu^I with heavier coinage metal ions results in tunable emissive arrays that are also stimuli-responsive. Thus, both linear multinuclear Cu^I and linear heteropolymetallic Cu^I/Ag^I as well as Cu^I/Au^I clusters are excellent candidates for applications in molecular/organic light-emitting devices (OLEDs). Alternatively, paramagnetic multinuclear cupric arrays are prominent as potential molecular wires with enhanced magnetic properties through multiple coupled d⁹ centers. This Review covers the whole range of linear multinuclear assemblies of cuprous and cupric ions in complexes and coordination polymers, their syntheses, photophysical behavior, and magnetic properties. Moreover, recent advances in the rapidly progressing field of hetero-Cu^I/Ag^I and Cu^I/Au^I molecular strings are also discussed.     

4,4'-联吡啶桥联的三个铜有机膦酸配合物的合成、结构及磁性

在水热条件下,以N-氧化-2-吡啶膦酸(H₂L)为主配体,4,4’-联吡啶(bpy)为桥联配体,合成了3个铜有机膦酸配合物：{[Cu(L)(bpy)_0.5(H₂O)]·2H₂O}_n(1),{[Cu(HL)₂(bpy)]·4H₂O}_n(2)和{[Cu₂(L)₂(bpy)]·3H₂O}_n(3)。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu(HL)₂]被bpy连接成一维链。配合物3中,四聚体[Cu₂(L)₂]₂被bpy连接成“砖块状”结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。     

4,4'-联吡啶桥联的三个铜有机膦酸配合物的合成、结构及磁性

在水热条件下,以N-氧化-2-吡啶膦酸（H2L）为主配体,4,4＇-联吡啶（bpy）为桥联配体,合成了3个铜有机膦酸配合物： {[CuL（bpy）0.5（H₂O）]·2H₂O}_n（1）, {[Cu（HL）₂（bpy）]·4H₂O}_n（2）和{[Cu₂（L）₂（bpy）]·3H₂O}_n（3）。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu（HL）₂]被bpy连接成一维链。配合物3中,四聚体[Cu₂（L）₂]₂被bpy连接成“砖块状”结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。     

三个基于Wells-Dawson型多酸的三核铜簇的合成、结构及性能

在水热条件下,通过Wells-Dawson型多酸[As_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(4-吡啶基)-1H-四氮唑(4-ptz)的反应,在同一反应釜中合成出2个结构完全不同的、都包含三核铜簇的多酸基化合物[Cu3(4-ptz)4(H_2O)7(As_2W_(18)O_(62))]·42H_2O(1)和[Cu3(4-ptz)5(H_2O)5(As_2W_(18)O_(62))]·47H_2O(2);当我们以另一种Wells-Dawson型多酸[P_2W_(18)O_(62)]6-、氯化铜(CuCl_2·2H_2O)和5-(3-吡啶基)-1H-四氮唑(3-ptz)反应,获得了另一种多酸基三核铜簇化合物[Cu3(3-ptz)4(H_2O)8(P_2W_(18)O_(62))]·33H_2O(3)。X射线单晶衍射结果表明,化合物1为多酸单支撑三核铜簇的悬臂式结构,化合物2的多阴离子被三核铜簇交替连接形成一维链式结构,而化合物3为多阴离子和三核铜簇形成的孤立结构。吡啶-四氮唑类配体(3-ptz和4-ptz)是形成化合物1~3中三核铜簇的重要结构因素。同时,研究了3个化合物的电化学以及光催化性能。     

Syntheses and Crystal Structures of Lanthanide Complexes of New 15-Membered Macrocyclic Ligands with Three Pendant Acetato Groups

Two new 15-memhored fimctionalized macrocycles, dioxo-polyazacydoalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhy-dride (DTPA = diethylenetrlamlnepentaacetic acid ) with 1,2-di-amlnopropane, ( 15-DTPA-1, 2-pn), or 1, 2-diaminocydohex-ane, (15-DTPA-1,2-cy). Their lanthanide complexes [ Ln ( 15-DTPA-1,2-pn)(H2O)]2[Ln= Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H2O)]2[Ln= Eu (3), Gd (4)] were also pre-pared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state;each metal ion is nine-coordinated in a distorted tricapped-trig-onal prism. In complex 4, the coexistence of two diastereoiso-meric molecules in the crystal lattice was observed.     

17电子钒开环夹心羰基配合物的合成及XRD,IR,EPR研究

以４种甲基取代戊二烯基为配体合成了４个过渡金属钒开环夹心羰基配合物［２，４－（ＣＨ３）２Ｃ５Ｈ５］２ＶＣＯ（Ｉ），［２，３－（ＣＨ３）２Ｃ５Ｈ５］ＶＣＯ（Ⅱ），［２－ＣＨ３Ｃ５Ｈ６］２ＶＣＯ（Ⅲ）和［３－ＣＨ３Ｃ５Ｈ６］２ＶＣＯ（Ⅳ），其中Ⅱ，Ⅲ，Ⅳ为新配合物，用Ｘ射线单晶衍射，ＩＲ，ＥＰＲ法对所合成配合物进行了结构表征，发现Ｉ具有两种晶相。     

Modular Assembly of Host–Guest Metal–Phenolic Networks Using Macrocyclic Building Blocks

The manipulation of interfacial properties has broad implications for the development of high‐performance coatings. Metal–phenolic networks (MPNs) are an emerging class of responsive, adherent materials. Herein, host–guest chemistry is integrated with MPNs to modulate their surface chemistry and interfacial properties. Macrocyclic cyclodextrins (host) are conjugated to catechol or galloyl groups and subsequently used as components for the assembly of functional MPNs. The assembled cyclodextrin‐based MPNs are highly permeable (even to high molecular weight polymers: 250–500 kDa), yet they specifically and noncovalently interact with various functional guests (including small molecules, polymers, and carbon nanomaterials), allowing for modular and reversible control over interfacial properties. Specifically, by using either hydrophobic or hydrophilic guest molecules, the wettability of the MPNs can be readily tuned between superrepellency (>150°) and superwetting (ca. 0°).     

基于钒氧多酸与大环铜配合物构筑的三维配位聚合物的合成与表征(英文)

通过[CuL](ClO4)2(L=5,12-二甲基-1,8-二乙醇基-1,3,6,8,10,13-六氮杂环十四烷)与NH4VO3反应,得到一个钒氧多酸桥联大环铜配合物的三维配位聚合物{[CuL][VO3]2·0.67H2O}n。并对其进行了元素分析、红外光谱、紫外光谱、热重和X-射线单晶衍射测定。单晶结构测试结果表明配合物属于三方晶系,R3空间群。在晶体结构中,铜原子与大环配体上的4个氮原子和钒氧四面体[VO4]中的2个氧原子配位,形成畸变的八面体构型。钒氧多酸阴离子[V6O18]6-桥联大环配合物[CuL]2+形成一个具有一维通道的三维配位聚合物。     

基于钒氧多酸与大环铜配合物构筑的三维配位聚合物的合成与表征

通过[CuL](ClO₄)₂(L=5,12-二甲基-1,8-二乙醇基-1,3,6,8,10,13-六氮杂环十四烷)与NH₄VO₃反应,得到一个钒氧多酸桥联大环铜配合物的三维配位聚合物{[CuL][VO₃]₂·0.67H₂O}_n。并对其进行了元素分析、红外光谱、紫外光谱、热重和X-射线单晶衍射测定。单晶结构测试结果表明配合物属于三方晶系,R3空间群。在晶体结构中,铜原子与大环配体上的四个氮原子和钒氧四面体[VO₄]中的2个氧原子配位,形成畸变的八面体构型。钒氧多酸阴离子[V₆O₁₈]^6-桥联大环配合物[CuL]²⁺形成一个具有一维通道的三维配位聚合物。     

Template Syntheses and Crystal Structures of Hexaaza Macrocyclic Complexes with C-Methyl Substituents

1 INTRODUCTION Polyaza-macrocyclic compounds with functional substituents have been extensively investigated recen- tly because of their potential applications in radioac- tive therapy, recovery of metal ions, biomimetic che- mistry, and catalysis[1, 2]. With various structures and distinctive properties, they have become significant building blocks for further chemical studies[3～6]. As far as the preparation method is concerned, metal template condensation reactions are shown to be effec…     

二维大环网状结构的双(三环已基锡)二元酸酯的合成、结构及生物活性

三环己基氢氧化锡分别与辛二酸和壬二酸进行甲醇溶剂热反应,合成了2个双(三环已基锡)二元酸酯(CH₂)_n(CO₂SnCy₃)₂[(n:6(1),7(2)],并用IR、¹H和¹³C NMR、元素分析和X射线单晶衍射表征结构。化合物1、2均属单斜晶系,空间群分别为P2₁/n和P2₁/c,在化合物的晶体中,1通过Sn-O共价键,2通过Sn-O和Sn…O弱作用,分别形成了四锡核30元(1)和32元(2)二维大环网状结构。化合物1、2对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有良好的体外抑制活性,对S. Aureus、B. Subtilis、E. Coli和S. Typhi具有选择性的抑菌作用。