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1.
《Journal of Coordination Chemistry》2012,65(18):2999-3007
Hydrothermal reactions of CuCN, K3[Fe(CN)6] with 2,2′-bipyridine, 1,10-phenanthroline or 2,6-bis(1,2,4-triazolyl)pyridine (btp) afford three coordination polymers, [Cu7(CN)7(bipy)2] n (1), [Cu2(CN)2(phen)] n (2) and [Cu3(CN)3(btp)] n (3). Complex 1 displays 1D polymeric ribbons which are assembled through Cu ··· Cu and π–π stacking interactions into a 3D framework. Complex 2 shows a 1D zigzag chain structure in which phen is a side ligand. In 3, the copper cyanide 2D polymeric networks are connected by tridentate btp to form a 3D metal-organic framework. These coordination polymers exhibit strong fluorescent emissions in the solid state. 相似文献
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The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(μ-Br)(Br)L](2) (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S-S, S-C(sp(2)), and C(sp(2))-N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym(2)S(2) and CuI leads to the formation of [Cu(3)I(pymS)(2)](n) (3) and [CuI(pym(2)S(3))] (pym(2)S(3) = pyrimidiltrisulfide) (4), while [Cu(3)Br(pymS)(2)](n) (5) is isolated in the reaction with CuBr(2). Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH(2)Cl(2):CH(3)CN at different ratios, 1:1 or 2:1, give the polymers [Cu(2)I(2)(pymSH)(2)](n) (6) and [Cu(2)I(2)(pymSH)](n) (7), respectively. The structure of the new compounds has been determined by X-ray diffraction. The studies of the physical properties of the novel coordination polymers reveal that compounds 3 and 5 present excellent electrical conductivity values at room temperature, while compounds 1, 3, and 5-7 show luminescent strong red emission at room temperature. 相似文献
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An interlocked M_4 L_8 coordination cage was synthesized by coordination-driven self-assembly of palladium(Ⅱ) ions with aromatic amide bidentate ligands.The reaction of the ligand and the metal at 2:1 ratio led to the monomeric M_2 L_4 cage as the kinetic product,while the thermodynamic product M_4 L_8 cage was obtained by prolongating the reaction.This conve rsion and the interlocked structure was clearly revealed by using ~1 H NMR,mass spectrometry and X-ray crystallography.The driving force of interlocking was mainly attributed to the interactions(hydrogen bonding,aromatic stacking and electrostatic interaction) arising from the aptitude of flexibility of the amide ligand. 相似文献
4.
Xu X Maresca KJ Das D Zahn S Zubieta J Canary JW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(24):5679-5683
The ligand in [Cu(6)CH3CN]-(ClO4)2 adopts two conformations that may be described as "pseudo-enantiomers" in that they possess approximately mirror-image molecular helicity, although they differ in the orientation of a single methyl substituent. The two conformations differ in energy as judged by analogy to other compounds studied previously, computation of the relative free energies of formation of the isomers, and measurement of solution circular dichroism spectra. The solid-state structures of both single enantiomer and racemic forms of the complex were determined by X-ray crystallography. In the chiral complex, a quasi-racemate was observed with both pseudo-enantiomeric conformers present in the asymmetric unit. Packing forces induce a higher energy conformation in order to achieve higher apparent symmetry in the solid state. In contrast, the racemic complex only displayed a single conformation corresponding to the lower energy one of the two observed in the single enantiomer structure. 相似文献
5.
ZHONG DiChang & LU TongBu Key Laboratory of Bioinorganic Synthetic Chemistry Ministry of Education State Key Laboratory of Optoelectronic Materials Technologies School of Chemistry Chemical Engineering Sun Yat-Sen University Guangzhou China Key Laboratory of Organo-Pharmaceutical Chemistry of Jiangxi Province College of Chemistry & Life Science Gannan Normal University Ganzhou 《中国科学B辑(英文版)》2011,(9)
During the last two decades,porous coordination polymers(PCPs),usually called as metal-organic frameworks(MOFs),have been developed rapidly due to their versatile structural diversities and potential physical and chemical functions.This article provides a short review of recent advances in the design and constructions of porous coordination polymers based on three planar rigid ligands,including imidazole-4,5-dicarboxlate(H3IDC),1H-tetrazole(HTz),as well as 1H-tetrazole-5-carboxylate(H2Tzc).Their preparation... 相似文献
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Lanthanide-transition metal (Ln-M) coordination polymers have attracted extensive interest because they exhibit novel physical properties originating from the interactions between distinct metal ions. This review mainly describes our recent work in the design of Ln-M coordination polymers through the assembly of different metal ions and organic ligands, especially the ligands with multiple N- and O-donor atoms. Many of these crystalline Ln-M materials exhibit intriguing structural motifs and interesting magnetic properties. 相似文献
9.
《Journal of Coordination Chemistry》2012,65(22):3583-3593
Four coordination polymers, [Ag(L1)](m-Hbdc) (1), [Ag(L1)]2(p-bdc)?·?8H2O (2), [Ag(Hbtc)(L1)][Ag(L1)]?·?2H2O (3) and [Ag2(L2)2](OH-bdc)2?·?4H2O (4), where L1?=?1,1′-(1,4-butanediyl)bis(imidazole), L2?=?1,2-bis(imidazol-1-ylmethyl)benzene, m-H2bdc?=?1,3-benzenedicarboxylic acid, p-H2bdc?=?1,4-benzenedicarboxylic acid, H3btc?=?1,3,5-benzenetricarboxylic acid, and OH–H2bdc?=?5-hydroxisophthalic acid, were synthesized under hydrothermal conditions. Compound 1 contains a–Ag-L1–Ag-L1–chain and a hydrogen-bonding interaction induced–(m-Hbdc)-(m-Hbdc)–chain. Compound 2 consists of two independent–Ag-L1–Ag-L1–chains. P-bdc anions are not coordinated. Hydrogen bonds form a 3D supramolecular structure. A novel (H2O)16 cluster is formed by lattice water molecules in 2. Compound 3 contains a–Ag-L1–Ag-L1–and a–Ag(Hbtc)-L1–Ag(Hbtc)-L1–chain. The packing diagram shows a 2D criss-cross supramolecular structure, with?π?···?π?and C–H ···?π?interactions stabilizing the framework. Compound 4 contains a [Ag2(L2)2]2+ dimer with hydrogen-bonding,?π?··· π, and Ag ··· O interactions forming a 3D supramolecular framework. The luminescent properties for these compounds in the solid state are discussed. 相似文献
10.
Reaction of copper(II) tetrazolate-5-carboxylate with different neutral N-donor spacer ligands under hydrothermal conditions leads to the formation of five new coordination polymers, [Cu(tzc)(pyz)(0.5)(H(2)O)(2)](n)·H(2)O (1), [Cu(tzc)(pyz)](n) (2), [Cu(tzc)(pym)(H(2)O)](n) (3), [Cu(tzc)(dpe)(0.5)(H(2)O)](n) (4) and [Cu(tzc)(azpy)(0.5)(H(2)O)](n) (5) (tzc = tetrazolate-5-carboxylate, pyz = pyrazine, pym = pyrimidine, dpe = 1,2-di(4-pyridyl)ethylene and azpy = 4,4'-azopyridine). All five structures were characterized by X-ray single-crystal measurements and bulk material can be prepared phase pure in high yields. The crystal structures of the hydrates 1, 3, 4 and 5 show dimeric [Cu(2)(N(tzc)-N(tzc))(2)] building units formed by μ(2)-N1,O1:N2 bridging tzc ligands as the characteristic structural motif. These six-membered entities in 1, 4 and 5 are connected by μ(2)-N,N' bridging N-donor ligands into 1D chains and in 3 into 2D layers. In the crystal structure of compound 2 adjacent Cu(II) cations are connected by μ(2)-N1,O1:N4,O2 bridging tzc ligands into chains, which are further connected by μ(2)-N,N' bridging pyz ligands forming 2D layers. Extensive hydrogen bonds in all compounds play an important role in the construction of their supramolecular networks. Investigations of their thermal properties reveal water release upon heating according to the formation of anhydrates before starting decomposing above 220 °C. Furthermore, the magnetic properties have been studied leading to consistent global antiferromagnetic exchange interactions with coupling constants of J = 3 ± 1 cm(-1) and long-range antiferromagnetic ordering states at lower temperatures. 相似文献
11.
The coordination properties of three heterofunctional phosphine oxide ligands, 2-methylpyridyldiphenylphosphine oxide (L1), phenylphosphino-bis-2-methylpyridine oxide (L2) and phenylphosphino-bis-2-methylpyridine N,N′,P-trioxide (L3) with Cu(II) is described. The X-ray crystal structures of the compounds display a distorted octahedral geometry, which exhibit Jahn–Teller distortions. In compounds 1 and 2, the L1 and L2 ligands react with Cu(BF4)2 in a 2:1 ligand to metal ratio, respectively, with the BF4 anions interacting with the metal center. L3 reacts with Cu(BF4)2 in 1:1 and 2:1 ligand/metal ratios to form compounds 3 and 4, respectively. Addition of either 2,2′-bipyridine or 4,4′-bipyridine to reaction solutions containing Cu(BF4)2 and L3 produces a discrete molecule (5) and a polymeric structure (7), respectively. The reaction of both bipyridines in the presence of Cu(BF4)2 and L3 gives rise to a discrete molecule (6) characterized by two octahedral coppers interconnected by the 4,4′-bipyridine. The electrochemical and photophysical properties of all compounds were investigated by cyclic voltammetry (CV) and UV–Vis, as they exhibited no emission or excitation in fluorimetric experiments. 相似文献
12.
Six mixed-valence Cu(I)Cu(II) compounds containing 4'-(4-pyridyl)-2,2':6',2' '-terpyridine (L1) or 4'-(2-pyridyl)-2,2':6',2' '-terpyridine (L2) were prepared under the hydrothermal and ambient conditions, and their crystal structures were determined by single-crystal X-ray diffraction. Selection of CuCl(2).2H(2)O or Cu(CH(3)COO)(2).H(2)O with the L1 ligand and NH(4)SCN, KI, or KBr under hydrothermal conditions afforded 1-dimensional mixed-valence Cu(I)Cu(II) compounds [Cu(2)(L1)(mu-1,1-SCN)(mu-Cl)Cl](n) (1), [Cu(2)(L1)(mu-I)(2)Cl](n) (2), [Cu(2)(L1)(mu-Br)(2)Br](n) (3), and [Cu(2)(L1)(mu-1,3-SCN)(2)(SCN)](n)(4), respectively. Compound 5, prepared by layering with CuSCN and L1, is a 2-dimensional bilayer structure. In compounds 1-5, the L1 ligand and X (X = Cl, Br, I, SCN) linked between monovalent and divalent copper atoms resulting in the formation of mixed-valence rectangular grid-type M(4)L(4) or M(6)L(6) building blocks, which were further linked by X (X = Cl, Br, I, SCN) to form 1- or 2-dimensional polymers. The sizes of M(4)L(4) units in 1-4 were fine-tuned by the sizes of X linkers. Reaction of Cu(CH(3)COO)(2).H(2)O with L2 and NH(4)SCN under hydrothermal conditions gave mixed-valence Cu(I)Cu(II) compound [Cu(2)(L2)(mu-1,3-SCN)(3)](n) (6). Unlike those in 1-5, the structure of 6 was constructed from thiocyanate groups and the pendant pyridine of L2 left uncoordinated. The temperature-dependent magnetic susceptibility studies on compounds 1 and 4 showed the presence of mixed-valence electronic structure. 相似文献
13.
Abdul-Kadir M Hanton LR Sumby CJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(45):12374-12380
A series of metallo-macrocyclic based coordination polymers has been prepared from flexible amide ligands N-6-[(3-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic acid (L1-CH(3)) and N-6-[(4-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic acid (L2-CH(3)). In all but one case, self-assembled dinuclear metallo-macrocyclic units form the basis of the polymeric structures, whereby discrete metal centres, and dinuclear or trinuclear clusters, are linked by the self-assembled macrocycles to give 1D and 2D coordination polymers. In one instance, a 1D coordination polymer is formed in a reaction carried out under ambient conditions; when the same reaction is conducted under solvothermal conditions a 2D structure is formed. In all but two of these structures, the polymeric chains and nets are close-packed within the crystals. In the case of a 6,3-connected 2D coordination polymer {[Cd(3)(L2-CH(3))(3)(NO(3))(L2)(CH(3)OH)](NO(3))(2)·12?H(2)O}(n) (9), small oval channels percolate down the a-axis of the unit cell. 相似文献
14.
Lei Shen Qian-Qian Ma Qing Liu Tian-Tian Jia Yue Xu Ting Zhu Dun-Ru Zhu Jie Yang 《Journal of the Iranian Chemical Society》2018,15(3):637-647
Six new complexes [Mn8(μ4-O)4(phpz)8(MeOH)4]·(MeOH)(H2O) (1) [Co2(HphpzH)(Hphpz)2(phpz)2]·4(MeOH) (2), Ni(Hphpz)2 (3), [Ni(Hphpz)2]·H2O (4), [Zn4(pzpy)4Cl4] (5) and [Cu2(pzpy)2(HCO2)2(H2O)2] (6) have been synthesized by hydrothermal reactions of MCl2·4H2O (M = Mn, Co, Ni, Zn or Cu) with 5-(2-hydroxyphenyl)-3-pyrazole (HphpzH) or 2-(1H-pyrazol-3-yl)pyridine (Hpzpy). The complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 is an octanuclear Mn(III) cluster, complexes 2 and 6 are binuclear Co(III) and Cu(II), respectively, complexes 3 and 4 are isomorphous mononuclear species, while complex 5 is a tetranuclear Zn(II) cluster. The magnetic behavior of complex 1 was investigated. Magnetic susceptibility measurements revealed antiferromagnetic exchange interactions between the metal centers in the clusters. The luminescence properties of the complexes were investigated at room temperature in the solid state. 相似文献
15.
M. D. Revenko N. V. Gérbéléu K. M. Indrichan 《Theoretical and Experimental Chemistry》1985,21(5):577-580
The passage of dry gaseous hydrogen chloride through chloroform solutions or acetone suspensions of S-substituted N1,N4-di(salicylidene)isothiosemicarbazidates of nickel (Ni(LRR)) has led to a demetallization reaction with the liberation in the free state of S-substituted N1,N4-di(salicylidene)isothiosemicarbazides with the general formula N2LRR (where R is H and R is CH3 (I); R is H and R is C2H5 (II); R is H and R is C3H7 (III); R is H and R is C7H7 (IV); and R is CH3 and R is CH3 (V)). The IR spectra of (I-IV) each showed bands characteristic for an aromatic ring and groups in the 1600–1500 cm–1 region, with a band of the deformation vibrations of an OH group at 1300 cm–1. The PMR spectra in CDCl3 each had two singlets at 12.15-11.25 and 9.00-8.36 ppm which were assigned, respectively, to the protons of an OH group and those of a =CH group. A multiplet in the 7.70-6.83 ppm region belonged to the protons of benzene rings. In the region of lower fields there were the signals of the substituents R and R. In the mass spectra of (I-V), the peaks of the molecular ions, and also the characteristic fragments OH, R, SR, and HSR have been detected.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 604–608, September–October, 1985. 相似文献
16.
G. V. Romanenko N. V. Podberezskaya N. V. Pervukhina 《Journal of Structural Chemistry》1993,34(3):440-468
Conclusions Due to a recent expansion of research into metal complexes with stable NR connected with prospects for the production of a radically new class of magnetic materials [50, 51], a great amount of data has been accumulated, in particular, on CC with anionic NR ligands. But until recently there were no reviews analyzing the structural features of these compounds. The reason for this is, evidently, dissimilarity of both the NR ligands and the CC based on them. The systematic studies on the synthesis, crystal structures, and magnetic properties of CC with 3-imidazoline NR permitted analysis of the crystallochemical structure of compounds. As the present paper is virtually the first publication that overviews structural studies of CC with NR, we did not undertake to give a complete analysis of the structure-property relationship. Nevertheless, the structural data obtained for CC with 3-imidazoline NR allow one to make some correlations between the character of exchange interactions and the electronic and spatial structure of CC [6, 7, 31].It is known that to choose an exchange cluster model, one needs information on the relative arrangement of PMC. But the quantum-chemical calculations of the electronic states of a system require exact data on the stereochemistry of a coordination unit and mutual arrangement of PMC. Besides, it should be noted that the relationship between crystal symmetry (centrosymmetric or acentric space group) and magnetic properties will not become adequate unitl crystal structure and symmetry studies have been carried out in a magnetic field at appropriate temperatures, i.e., under conditions of measurement of magnetic parameters for compounds of a given class.In the near future, this research will certainly be continued, both in the field of synthesis of CC with 3-imidazoline NR and preparation of their single crystals, and in the field of studies on their structure, magnetic and other physical properties, as well as of quantum-chemical calculations.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhumal Strukturnoi Khimii, Vol. 34, No. 3, May–June 1993.Translated by T. Yudanova 相似文献
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Zi‐Long Yue Yu‐Quan Feng Seik Weng Ng 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(2):100-102
In the linear coordination polymer catena‐poly[[[aqua(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ4O2:O2′,N,O6‐[(nitrato‐κ2O,O′)bismuth(III)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ4O2,N,O6:O6′] dihydrate], {[BiIIICuII(C7H3NO4)2(NO3)(C12H8N2)(H2O)]·2H2O}n, the BiIII cation is O,N,O′‐chelated by the two pyridine‐2,6‐dicarboxylate ligands and O,O′‐chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine‐2,6‐dicarboxylate ligand uses one of its carboxylate O atoms to bind to an aqua(1,10‐phenanthroline)copper(II) unit, the Cu—O dative bonds giving rise to the formation of a ribbon motif. The CuII cation exhibits a square‐pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water molecules are hydrogen bonded to the same ribbon. 相似文献
19.
Lei Shen Meng Jie Cao Fei Fei Zhang Qi Wu Li Yang Zhao Yi Ming Lu Qiao Yun Li Gao Wen Yang Bo Wei Jian Hua Zou 《Transition Metal Chemistry》2016,41(2):125-131
Reactions of three tetrazole carboxylate ligands, namely 5-(4-pyridyl)tetrazole-2-acetic acid (Hpytza), 1,3,5-tris(tetrazol-5-yl)benzene-N2,N2′,N2″-triacetic acid (H3tzpha) and 5-aminotetrazole-1-propanoic acid (Hatzpa) with Mn(NO3)2·6H2O in the presence of KOH afforded three new complexes, [Mn(pytza)2] (1), [Mn3(tzpha)2(H2O)12]·2CH3OH·10H2O (2) and [Mn(atzpa)2(H2O)2] (3), respectively. These complexes were characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Complex 1 displays a three-dimensional network while 2 and 3 show one-dimensional chains. Furthermore, the luminescence properties of these complexes were investigated at room temperature in the solid state. 相似文献
20.
Gibson SE Ibrahim H Pasquier C Peplow MA Rushton JM Steed JW Sur S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):269-276
Metal isocyanides have been used and studied by organometallic chemists for many years and, as a result, they have a rich and interesting chemistry. The nature of metal-free isocyanides and the methods of making isocyanide complexes, however, has resulted in the vast majority of studies to date being performed with structurally simple isocyanides. We report here a new approach to the synthesis of isocyanide ligands that involves the reaction of a metal carbonyl ligand with the anion of a phosphoramidate. As phosphoramidates can be synthesised in one step from amines, our method means that the structural diversity of readily available amines, particularly chiral amines, can now be incorporated into isocyanide ligands. 相似文献