三唑-芳香多羧酸类混配金属配合物的结构与磁性能研究

以三唑为主配体的过渡金属配合物以其结构多样性及在磁性、吸附等功能材料中的潜在应用而成为众多科研工作者的研究热点内容之一．本文从三唑一芳香多羧酸混配配合物的合成以及芳香酸对配合物中金属一三唑次级结构的调节角度,总结了近年来报道的该类混配金属配合物的结构多样性．在此基础上,初步关联了该类混合配体顺磁金属配合物的磁一构关系．     

Merging porphyrins with organometallics: synthesis and applications

The coordination chemistry of porphyrins has traditionally involved the ability of the porphyrin's tetrapyrrolic core to accommodate metal ions of varying charges and sizes, and on the organometallic chemistry of the resulting metalloporphyrins. However, the organometallic chemistry of porphyrins is not necessarily restricted to the metal bound in the porphyrin core, but can also be extended to the porphyrin periphery, be it through direct metalation of the porphyrin macrocycle at the meso or beta position, or by attachment to or merger of the porphyrin skeleton with ligands, followed by metalation. This Review focuses on the synthetic strategies used for porphyrins with peripheral metal-carbon bonds. The exciting results that have been produced underscore the importance and future potential of this field.     

MALDI-TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in

A mini-review of the characterisation of metal-containing compounds by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is presented. Organometallic and coordination compounds have many varied applications, most notably in industrial catalytic processes and also in the electronics and healthcare sectors. In general, the compounds discussed, be they small or large molecules, have a high percentage metal content, rather than simply containing 'a metal atom'. A brief history of the field is given, but the main scope over the last 5 years is covered in some detail. How MALDI-TOFMS compliments electrospray for metal-containing compounds is highlighted. Perspectives on recent advances, such as solvent-free and air/moisture-sensitive sample preparation, and potential future challenges and developments, such as nanomaterials and metallodrug/metallometabolite imaging, are given.     

The reactions of Cr(CO)6, Fe(CO)5, and Ni(CO)4 with O2 yield viable oxo‐metal carbonyls

Transition metal complexes with terminal oxo and dioxygen ligands exist in metal oxidation reactions, and many are key intermediates in various catalytic and biological processes. The prototypical oxo‐metal [(OC)₅Cr? O, (OC)₄Fe? O, and (OC)₃Ni? O] and dioxygen‐metal carbonyls [(OC)₅Cr? OO, (OC)₄Fe? OO, and (OC)₃Ni? OO] are studied theoretically. All three oxo‐metal carbonyls were found to have triplet ground states, with metal‐oxo bond dissociation energies of 77 (Cr? O), 74 (Fe? O), and 51 (Ni? O) kcal/mol. Natural bond orbital and quantum theory of atoms in molecules analyses predict metal‐oxo bond orders around 1.3. Their featured ν(MO, M = metal) vibrational frequencies all reflect very low IR intensities, suggesting Raman spectroscopy for experimental identification. The metal interactions with O₂ are much weaker [dissociation energies 13 (Cr? OO), 21 (Fe? OO), and 4 (Ni? OO) kcal/mol] for the dioxygen‐metal carbonyls. The classic parent compounds Cr(CO)₆, Fe(CO)₅, and Ni(CO)₄ all exhibit thermodynamic instability in the presence of O₂, driven to displacement of CO to form CO₂. The latter reactions are exothermic by 47 [Cr(CO)₆], 46 [Fe(CO)₅], and 35 [Ni(CO)₄] kcal/mol. However, the barrier heights for the three reactions are very large, 51 (Cr), 39 (Fe), and 40 (Ni) kcal/mol. Thus, the parent metal carbonyls should be kinetically stable in the presence of oxygen. © 2014 Wiley Periodicals, Inc.     

Transition metal coordination complexes based on V-shaped bis-triazole ligand: syntheses,structures, and properties

Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO₃)₂ (M = Co²⁺ (1), Cu²⁺ (2)) afforded two new coordination polymers, [Co(btb)₂(NO₃)(H₂O)]_n·NO₃·H₂O (1) and [Cu(btb)₂(NO₃)₂]_n (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in the space group P2₁/m and 2 crystallizes in the space group Pī, both showing a double-stranded chain structure. The 1-D chains are interconnected via π?π interactions to lead to 2-D ladder-like supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2 have been investigated. For 1, weak antiferromagnetic interactions are observed at low temperature, and the data obey the Curie–Weiss law χ_M = C/(T?θ), with C = 3.22 cm³·mol^?1·K and θ = ?10.39 K. For 2, the decrease of the χT vs. T curve at low temperature is the result of intermolecular antiferromagnetic magnetic interactions.     

Syntheses,structures and properties of four second-sphere coordination complexes via metal halide anion and naphthalene-based ligand

Second-sphere coordination refers to any intermolecular interactions with the ligands directly bound to the primary coordination sphere of a metal ion. Four supramolecular complexes, 0.5[L·2H]²⁺·0.5[MCl₄]^2?·[CH₃OH]·0.5[CH₂Cl₂] (M = Co, crystal 1; M = Mn, crystal 2), 0.5[L·2H]²⁺·0.5[ZnBr₄]^2?·[CH₃OH]·0.5[CH₂Cl₂] (crystal 3), and 0.5[L·2H]²⁺·0.5[Cu₂Br₄]^2?·H₂O (crystal 4), based on naphthalene-based ligand N,N,N′,N′-tetra-p-methylnaphthyl-ethanediamine (L), have been synthesized. X-ray analysis reveals that 1–3 are isostructural, in which the methanol molecules are bridges, connecting the protonated L and metal chloride anions via N–H?O and O–H?Cl (Br) interactions to construct the host framework, and forming X-shaped cavity accessible for the inclusion of weakly polar guest molecules of dichloromethane. Dichloromethane is connected with the host framework through van der Waals forces. In 4, a dinuclear anion [Cu₂Br₄]^2? is connected with the ligand through N–H?Br interactions, in which the water molecules are accommodated between chains formed by the ligand and [Cu₂Br₄]^2?. Structure stability, thermal analysis, and photoluminescent properties were studied for 1–4.     

The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers

A series of titanocene(III) alkoxides L₂Ti(III)OR where L = Cp, R = Et(1b), ^tBu(1a), 2,6-Me₂C₆H₃(1c), 2,6-^tBu₂-4-Me-C₆H₂(1d), or L = Cp*, R = Me(2e), ^tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)₃]₂ [M = Mo, W], [CpRu(CO)₂]₂, and Co₂(CO)₈. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)₃]₂ [M = Mo, W] to form heterobimetallic complexes L₂Ti(OR)(μ-OC)(CO)₂MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co₂(CO)₈ resulted in formation of Ti-Co₁ heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co₃ tetrametallic complexes, Cp₂Ti(O^tBu)(μ-OC)Co₃(CO)₉ from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.     

Syntheses,crystal structures,and properties of four new coordination compounds of transition metals and imidazoledicarboxylic acid derivatives

Four new transition metal coordination complexes, [Cd(H₂pimdc)₂(H₂O)₂]?·?4H₂O (1), [Zn(H₂pimdc)₂(H₂O)₂]₂?·?7H₂O (2), and [M(H₂pimdc)₂] (M?=?Cu (3) or Ni (4), H₂pimdc^??=?2-propyl-4,5-imidazoledicarboxylate), have been prepared by conventional synthesis and characterized by elemental analyses, IR, TG, and single-crystal X-ray diffraction. H₂pimdc^? is a bidentate chelating ligand in 1 and 2, leading to 3-D supramolecular structures through hydrogen bonds. However, H₂pimdc^? is a tridentate chelating-bridge ligand in 3 and 4, which exhibit 2-D layer structures. Thermal properties and photoluminescence spectra of 1–4 were measured.     

Gelatin-immobilized metal complexes: synthesis and applications

Formation of p-, d- and f-metal complex gelatin-immobilized matrix systems using reactions of electrophilic, nucleophilic substitution and template synthesis, and employment of these materials in photographic processes, in spectroscopy and for absorption of metal ions, have been summarized and discussed. The review covers the period 1990–2005.     

Some less usual properties of tetracyano complexes

The structure and reactivity of one unique molecule may be understood only in relation to its molecular surroundings. The non-stoichiometric forms of the tetracyano complexes M(B) _mM (CN)₄·nG (B=nitrogen or oxygen containing base; G=aromatic compound or H₂O,m0,n>0) are understood in this respect. Their stoichiometric or non-stoichiometric forms, with voids either completely or more often partially occupied, are responsible for their observed sorptive and resorptive abilities. The effects of the surroundings are correlated with the results of thermal analysis, magnetic measurements and their sorptive abilities.Dedicated to Professor H. M. Powell.     

The hapticity of cyclooctatetraene in its first row mononuclear transition metal carbonyl complexes: Several examples of octahapto coordination

The two cyclooctatetraene metal carbonyls that have been synthesized are the tetrahapto derivative (η⁴-C₈H₈)Fe(CO)₃ and the hexahapto derivative (η⁶-C₈H₈)Cr(CO)₃ using the reactions of cyclooctatetraene with Fe(CO)₅ and with fac-(CH₃CN)₃Cr(CO)₃, respectively. Related C₈H₈M(CO)_n (M = Ti, V, Cr, Mn, Fe, Co, Ni; n = 4, 3, 2, 1) species have now been investigated by density functional theory in order to explore the scope of cyclooctatetraene metal carbonyl chemistry. In this connection, the existence of octahapto (η⁸-C₈H₈)M(CO)_n species is predicted as long as the central metal M does not exceed the 18-electron configuration by receiving eight electrons from the η⁸-C₈H₈ ring. Thus the lowest energy structures (η⁸-C₈H₈)Ti(CO)_n (n = 3, 2, 1), (η⁸-C₈H₈)M(CO)_n (M = V, Cr; n = 2, 1), and (η⁸-C₈H₈)Mn(CO) all have octahapto η⁸-C₈H₈ rings. An exception is (η⁶-C₈H₈)Fe(CO), with a hexahapto η⁶-C₈H₈ ring and thus only a 16-electron configuration for the iron atom. Hexahapto (η⁶-C₈H₈)M(CO)_n structures are predicted for the known (η⁶-C₈H₈)Cr(CO)₃ as well as the unknown (η⁶-C₈H₈)Ti(CO)₄, (η⁶-C₈H₈)V(CO)₃, (η⁶-C₈H₈)Mn(CO)₂, and (η⁶-C₈H₈)Fe(CO)₂ with 18, 18, 17, 17, and 18 electron configurations, respectively, for the central metal atoms. There are two types of tetrahapto C₈H₈M(CO)_n complexes. In the 1,2,3,4-tetrahapto (η⁴-C₈H₈)M(CO)_n complexes two adjacent CC double bonds, forming a 1,3-diene unit similar to butadiene, are bonded to the metal atom. In the 1,2,5,6-tetrahapto (η^2,2-C₈H₈)M(CO)₃ derivatives two non-adjacent CC double bonds of the C₈H₈ ring are bonded to the metal atom. The known (η⁴-C₈H₈)Fe(CO)₃ is a 1,2,3,4-tetrahapto complex. The unknown isomeric 1,2,5,6-tetrahapto complex (η^2,2-C₈H₈)Fe(CO)₃ is predicted to lie ∼15 kcal/mol above (η⁴-C₈H₈)Fe(CO)₃. The related 1,2,5,6-tetrahapto complexes (η^2,2-C₈H₈)Cr(CO)₄, (η^2,2-C₈H₈)Mn(CO)₄, [(η^2,2-C₈H₈)Mn(CO)₃]⁻, (η^2,2-C₈H₈)Co(CO)₂, and (η^2,2-C₈H₈)Ni(CO)₂ are all predicted to be low-energy structures.     

Two novel benzenedicarboxylate‐metal complexes: synthesis,crystal structures and fluorescent properties

Two novel benzenedicarboxylate–metal complexes, [Sm(nphth)(Hnphth)(H₂O)₃^?H₂O]₂ and [Zn(nphth)(bipy)(H₂O) ?H₂O]₂ (2) (H₂nphth = 3‐nitrophthalic acid, bipy = 2,2′‐bipyridine), have been synthesized under hydrothermal condition and characterized by single‐crystal X‐ray diffraction. Both complex 1 and 2 exhibit a dimeric structure, and nphth ligand shows different coordination mode in the f‐block and d‐block complexes. The fluorescent properties of two complexes are investigated; the results reveal that the two complexes show different kinds of fluorescence. Copyright © 2007 John Wiley & Sons, Ltd.     

具有新颖嵌合作用的金属配合物的微波合成、晶体结构及性质研究

在微波辐射条件下合成了两种新的离子液体金属配合物[Ni(m-HNDA)2(H2O)4](1),[Zn(m-HNDA)2(H2O)4]·H2O(2),用元素分析、红外光谱、紫外光谱对它们进行了表征,通过X射线单晶衍射测定了它们的晶体结构.在晶体结构中,标题物通过基团间的嵌合作用,π-π相互作用和分子间氢键自组装成了三维网状的多孔结构.由氢键和π-π相互作用的强弱推测标题物的稳定性次序2>1,与实测热稳定性次序完全吻合;电化学性质表明,金属的配位改变了配体的循环伏安性质.另外,两种配合物可在水溶液中高选择性的识别氟离子.     

Interfacial coordination chemistry. Current status and applications

After definitions of interfacial coordination chemistry (ICC) and surface organometallic chemistry (SOMC), their main characteristics and applications are compared. The common concepts of ICC and classical coordination chemistry, as well as the specific features of ICC are illustrated through some examples. Finally, possible applications of ICC to catalyst preparation, adsorption and relations to catalysis are given.     

Imidazolidinium ferrate complexes: Synthesis and catalytic properties

The new well-defined and air stable anionic iron complexes bearing an imidazolidinium ligand (2a–d) have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction studies. Starting from FeBr₂, [imidazolidinium][FeBr₄] complexes 2a and 2b were prepared. The reaction of imidazolidinium chlorides with Fe(OAc)₂, followed by a recrystallization in the air led to bis(imidazolidinium) μ-oxido-bis[trichloroferrate(III)] complexes 2c and 2d. The catalytic activity of these novel complexes has been evaluated in the cross-coupling reactions of alkyl halides with Grignard reagents.     

Design and synthesis of ion‐conductive polyphosphazenes for fuel cell applications: Review

New proton‐conductive fuel cell membranes have been produced by the linkage of acidic functional groups to aryloxy side units attached to a polyphosphazene macromolecular chain. The functional groups include sulfonic acid, phosphonic acid, and sulfonimide units. The different functional groups impart different water retention, proton conduction, and methanol resistance to the membranes. Special advantages are foreseen for uses in direct methanol fuel cells. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2358–2368, 2006     

四苯骈卟啉及其金属配合物的合成

卟啉类化合物作为电子给体在光合作用模拟研究中占据着重要位置 ,在卟啉环上引入供电子基团以增大共轭体系 ,常有利于卟啉环的给电子作用 ,过去常用的卟啉化合物为四苯基卟啉及其衍生物 ,但由于空阻作用 ,四个亚甲基上的苯基不能很好与卟啉环共平面而降低了共轭效应 ,为了寻求一种更有利于卟啉环共轭大Π键形成的结构 ,我们合成了比四苯基卟啉共平面效果更好的卟啉化合物———四苯骈卟啉 (Ｈ2 ＴＢＰ)及其与Ｎｉ2 + 、Ｃｏ2 + 、Ｚｎ2 + 的金属配合物以及研究它的给电子作用效果。四苯骈卟啉配合物早在 1 92 8年就为人们所认识[1] ,但其研…     

Review: the multicolored coordination chemistry of violurate anions

This review provides a comprehensive overview on the coordination chemistry of violuric acid, C₄H₃N₃O₄ (= H₃Vio), and its derivatives (e.g. 1,3-diorganovioluric acids and thiovioluric acid). The most remarkable property of these colorless compounds is the formation of brightly colored (pantochromic/polychromic) salts with colorless cations such as alkali metal and alkaline earth metal ions and organoammonium ions. These magnificent colors have fascinated chemists for more than a century. Only in recent years it has been fully recognized that the structural chemistry of violurates is rather interesting and diverse. Violurate anions are excellent building blocks for new supramolecular assemblies in the crystalline state. Various organoammonium violurates and transition metal violurate complexes have been structurally characterized through single-crystal X-ray diffraction. Highly characteristic for these structures is the formation of 1D, 2D, or 3D hydrogen-bonded assemblies in the crystalline state. This review provides a comprehensive overview on the multicolored coordination chemistry of violurate anions, with the focus being on structurally characterized species.     

Radical anion and coordination compounds of polyconjugated molecules:potential organic materials with unusual magnetic,conducting and optical properties

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