单核铜配合物[Cu~(II)(HIPP)(pydc)(H_2O)]的合成和晶体结构

用溶剂热合成方法合成了一个单核铜配合物CuII(HIPP)(pydc)(H2O),采用元素分析法和X射线单晶衍射法对该配合物的组成和结构进行了表征.配合物CuII(HIPP)(pydc)(H2O)属于正交晶系,空间群是Pbca.a=0.663 93(18)nm,b=2.062 2(6)nm,c=2.619 1(7)nm,α=90°,β=90°,γ=90°,V=3.585 9(17)nm3,Z=8,ρc=1.693g·cm-3,F(000)=1 864,GOF=0.882,R1=0.037 4,wR2=0.111 8[I2σ(I)].中心铜原子与配体脱质子2,6-吡啶二甲酸的2个羧基氧原子和1个氮原子、HIPP的1个氮原子和1个氧原子及1个水分子中的氧原子形成六配位的变形八面体.结构分析表明晶体中分子间含有氢键.     

Synthesis and X-ray crystal structures of Cs2[W(bpy)(CN)6]·2H2O and (AsPh4)2[W(bpy)(CN)6]·3.5H2O

The synthesis, spectral properties and crystal structures of Cs₂[W(bpy)(CN)₆]·2H₂O and (AsPh₄)₂[W(bpy)(CN)₆]·3.5H₂O are described. The anions of both salts show distorted antiprismatic geometry with very similar bond lengths and angles. The structure of the [W(bpy)(CN)₆]^2– anion is independent of the type of cation, in contrast to the octacyanotungstate(IV).     

A kinetic model for photoswitching of magnetism in the high spin molecule [Mo(IV)(CN)2(CN-Cu(II)(tren))6](ClO4)8

The heptanuclear complex [Mo(iv)(CN)(2)(CN-CuL)(6)](8+) switches from a paramagnetic dark state corresponding to six spin-1/2 Cu(ii) ions to a predominantly high spin S = 3 state, on prolonged irradiation with 406 nm laser radiation at low temperature. The system returns to a paramagnetic state on warming to room temperature. The temperature dependence of the chi(M)T vs. T curve depends upon duration of irradiation. An earlier microscopic model showed that the excitation cross sections in different spin manifolds are similar in magnitude and that photomagnetism is not due to preferential excitation to the S = 3 state. In this paper, we attribute photomagnetism to a long lived S = 3 charge transfer excited state for which there appears to be sufficient experimental evidence. Based on this postulate, we model the photomagnetism by employing a kinetic model which includes internal conversions and intersystem crossings. The key feature of the model is the assumption of the existence of two kinds of S = 3 states: one of which has no direct pathway for internal conversion and the other characterized by slow kinetics for internal conversion to the low-energy states. The trapped S = 3 state can decay via a thermally activated barrier to the other S = 3 state. The experimental chi(M)T vs. T for two different irradiation times are fitted using Arrhenius dependence of the rate constants in the model.     

Structure and magnetism of the tetra-copper(II)-substituted heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8-)

The novel heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8)(-) (1) has been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic studies. Single-crystal X-ray analysis was carried out on [K(7)Na[Cu(4)K(2)(H(2)O)(6)(alpha-AsW(9)O(33))(2)].5.5H(2)O](n)(K(7)Na-1), which crystallizes in the tetragonal system, space group P42(1)m, with a = 16.705(4) A, b = 16.705(4) A, c = 13.956(5) A, and Z = 2. Interaction of the lacunary [alpha-AsW(9)O(33)](9)(-) with Cu(2+) ions in neutral, aqueous medium leads to the formation of the dimeric polyoxoanion 1 in high yield. Polyanion 1 consists of two alpha-AsW(9)O(33) units joined by a cyclic arrangement of four Cu(2+) and two K(+) ions, resulting in a structure with C(2)(v)() symmetry. All copper ions have one terminal water molecule, resulting in square-pyramidal coordination geometry. Three of the copper ions are adjacent to each other and connected via two micro(3)-oxo bridges. EPR studies on K(7)Na-1 and also on Na(9)[Cu(3)Na(3)(H(2)O)(9)(alpha-AsW(9)O(33))(2)].26H(2)O (Na(9)-2) over 2-300 K yielded g values that are consistent with a square-pyramidal coordination around the copper(II) ions in 1 and 2. No hyperfine structure was observed due to the presence of strong spin exchange, but fine structure was observed for the excited (S(T) = 3/2) state of Na(9)-2 and the ground state (S(T) = 1) of K(7)Na-1. The zero-field (D) parameters have also been determined for these states, constituting a rare case wherein one observes EPR from both the ground and the excited states. Magnetic susceptibility data show that Na(9)-2 has antiferromagnetically coupled Cu(2+) ions, with J = -1.36 +/- 0.01 cm(-)(1), while K(7)Na-1 has both ferromagnetically and antiferromagnetically coupled Cu(2+) ions (J(1) = 2.78 +/- 0.13 cm(-)(1), J(2) = -1.35 +/- 0.02 cm(-)(1), and J(3) = -2.24 +/- 0.06 cm(-)(1)), and the ground-state total spins are S(T) = 1/2 in Na(9)-2 and S(T) = 1 in K(7)Na-1.     

Two new hybrid organic/inorganic copper(II)-oxovanadate(V) diphosphonates: [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O and [Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8. Synthesis, structure, and magnetic properties

Two new hybrid organic/inorganic copper oxovanadium diphosphonates [Cu2(phen)2(O3PCH2PO3)(V2O5)(H2O)] x H2O (1) and [(Cu2(phen)2(O3P(CH2)3PO3)(V2O5)] x C3H8 (2) have been obtained by hydrothermal synthesis. The compounds are monoclinic, and they crystallize in the space group P2(1)/n with cell parameters of a = 11.788(2) A, b = 17.887(3) A, c = 14.158(2) A, and beta = 93.99(0) degrees and in the space group C2/c with cell parameters of a = 11.025(1) A, b = 18.664(2) A, c = 15.054(2) A, and beta = 90.06(0) degrees, respectively. Both compounds present two-dimensional frameworks built up from infinite chains of corner-sharing vanadium tetrahedra and diphosphonate groups connected by copper tetramers for (1) and copper dimers for (2). The remarkable feature of (2) is the encapsulation of propane molecules, stabilized by strong hydrogen bonding between the layers. The magnetic properties of the compounds have been investigated showing antiferromagnetic coupling with Tmax = 64 K for (1) and Curie-like paramagnetic behavior for (2).     

Crystal structure of tetraphenylarsonium aquatetracyanonitridorhenate(V), (AsPh4)2 [ReN(H2O)(CN)4]·5H2O

The crystal structure of (AsPh₄)₂[ReN(H₂O)(CN)₄]·5H₂O has been determined from three-dimensional X-ray diffraction data. The yellow crystals are monoclinic, space group P2₁/n with cell dimensionsa=15.482(1),b=19.950(2),c=16.999(1)? and β=101.69(6)^o,Z=4,D _expt=1.48(1)g cm⁻³ andD _calc=1.52g cm⁻³. The anisotropic refinement of 7858 observed reflections converged toR=0.055. The [ReN(H₂O)(CN)₄]²⁻ ion has a distorted octahedral geometry. Bond distances: Re≡N=1.639(8), Re−OH₂=2.496(7) and Re−C_(av)=2.11(1) ?. The rhenium atom is displaced by 0.35 ? out of the plane formed by the four carbon atoms of the cyano ligands towards the terminal nitrido ligand. TMC 2479     

Synthesis,crystal structure,magnetic properties and electrochemical behavior of the mixed valence compound [CuI(CN)3CuII(dipn)]

A mixed-valence cyano-bridged Cu^II/Cu^I complex, 1, has been prepared. Complex 1 was fully characterized spectroscopically (UV-Vis and IR), and its structure was determined by X-ray crystallography. The magnetic property was measured in the temperature range 2–300?K. Electrochemical studies of 1 reveal a one-electron oxidation-reduction process associated with the Cu(II)/Cu(I) couple.     

One-dimensional magnetism and crystal structure ofcatena-di-bromobis(3,5-dimethylpyridine)copper(II)

Summary Crystals ofcatena-di--bromobis(3,5-dimethylpyridine)copper(II) are monoclinic, space group P2₁/a. The unit cell constants area=13.900(2),b=14.416(2),c=4.097(1) Å,=93.49(2)°, V=819.4 ų and Z=2. The structure was determined from powder data using a Guinier-Johansson focussing powder camera. The structure was solved using a simplex method for function minimization to a conventional R-value of 0.13.The structure consists of infinite linear chains parallel toc in which the copper coordination is distorted elongated octahedral. Cu-Br distances were found to be 2.449(7) and 3.286(7) Å, whereas the Cu-N bond length is 2.02(2) Å. All distances are in the range usually observed for this type of compounds.The antiferromagnetic superexchange interactions between adjacent Cu^II ions (J = –21 cm^–1) has been compared with those observed in structural similar CuBr₂L₂ compounds. The differences in observed J-values are discussed briefly, in relation to the structural variations. It appears that very small changes in structural parameters strongly affect the magnetic exchange.     

Peculiar field-dependent magnetic behavior of cyano-bridged coordination polymer Er(H2O)4[W(CN)8

The two-dimensional cyano-bridged coordination polymer Er(H(2)O)(4)[W(CN)(8)] exhibits a magnetic transition at 12 K and an unusual field-dependent transition from short-range to ferromagnetic ordering.     

Microwave-assisted construction of ferromagnetic coordination polymers of [W(V)(CN)8]3- with Cu(II)-pyrazole synthons

The microwave-mediated self-assembly of [W(V)(CN)(8)](3-) with Cu(II) in the presence of pyrazole ligand resulted in the formation of three novel assemblies: Cu(II)(2)(Hpyr)(5)(H(2)O)[W(V)(CN)(8)](NO(3))·H(2)O (1), {Cu(II)(5)(Hpyr)(18)[W(V)(CN)(8)](4)}·[Cu(II)(Hpyr)(4)(H(2)O)(2)]·9H(2)O (2), and Cu(II)(4)(Hpyr)(10)(H(2)O)[W(V)(CN)(8)](2)(HCOO)(2)·4.5H(2)O (3) (Hpyr =1H-pyrazole). Single-crystal X-ray structure of 1 consists of cyanido-bridged 1-D chains of vertex-sharing squares topology. The structure of 2 reveals 2-D hybrid inorganic layer topology with large coordination spaces occupied by {Cu(Hpyr)(2)(H(2)O)(4)}(2+) ions. Compound 3 contains two types of cyanido-bridged 1-D chains of vertex-sharing squares linked together by formate ions in two directions forming hybrid inorganic-organic 3-D framework (I(1)O(2)). The magnetic measurements for 1-3 reveal a weak ferromagnetic coupling through Cu(II)-NC-W(V) bridges.     

铜配合物[Cu_2(L)_2(SiW_(12)O_(40))(H_2O)_8]·H_2O的合成、结构与性质研究

利用水热合成技术制备了基于半刚性双吡啶双酰胺配体L(N,N′-双(4-吡啶甲酰胺)-1,2-环己烷)和Keggin型多金属氧酸盐的铜功能配合物[Cu_2(L)_2(Si W_(12)O_(40))(H_2O)_8]·H_2O,并通过元素分析、红外光谱和X-射线单晶衍射方法确定了该配合物的晶体结构.结构分析表明该化合物属于三斜晶系,P1-空间群,晶胞参数a=1.153 10(10)nm,b=1.339 10(12)nm,c=1.429 40(12)nm,α=71.514 0(10)°,β=66.926 0(10)°,γ=68.111 0(10)°,V=1.846 0(3)nm~3,Z=1,R_1=0.067 3,w R_2=0.181 1.配合物由离散的[Si W_(12)O_(40)]~(4-)杂多阴离子和[Cu_2(L)2(H_2O)_8]~(4+)阳离子组成,2种结构单元间通过氢键作用形成二维超分子层结构.标题配合物修饰的碳糊电极对NO~(2-)还原有较好的电催化活性,而且该配合物对降解亚甲蓝分子有显著的光催化效率.     

Assignment of the electronic spectra of [Mo(CN)(8)](4)(-) and [W(CN)(8)](4)(-) by Ab initio calculations

CASPT2 calculations are performed on the dodecahedral and square antiprismatic isomers of the [Mo(CN)(8)](4)(-) and [W(CN)(8)](4)(-) complexes. The high-energy experimental bands above 40000 cm(-)(1) are assigned to MLCT transitions. The experimental observed trend of the extinction coefficients for the molybdenum and tungsten complex is reproduced by our CASSCF oscillator strengths. All bands below 40000 cm(-)(1) can be ascribed to ligand-field transitions, although small contributions from forbidden MLCT transitions cannot be excluded. In order to account for all experimental bands in the electronic spectrum of these octacyanocomplexes, a dynamic equilibrium in solution between the two isomeric forms must be hypothesized. Spin-orbit coupling effects are found to be more important for the square antiprismatic isomers; in particular, large singlet-triplet mixings are calculated for this isomer of [W(CN)(8)](4)(-). Ligand-field and Racah parameters as well as spin-orbit coupling constants are determined on the basis of the calculated transition energies. The obtained values for these parameters support the recently proposed model for exchange interactions in magnetic clusters and networks containing pentavalent octocyanometalates of molybdenum and tungsten.     

The crystal structure of (AsPh4)2[OsN(OH)(CN)4]

Summary The crystal structure of (AsPh₄)₂[OsN(OH)(CN)₄] has been determined from three-dimensional X-ray diffraction data. The [OsN(OH)(CN)₄]^2– ion has a distorted octahedral geometry with bond distances: ON = 1.606(5), Os-OH = 2.123(5) and Os-C_av = 2.068(8) Å. The osmium atom is displaced 0.26 Å from the equatorial cyano-carbon atom plane.     

Synthesis and crystal structure of ionic multicomponent complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) containing C(60)(CN)(2).- radical anion and sigma-bonded diamagnetic Co(II)TPP(C(60)(CN)(2)) -anion

The ionic multicomponent complex complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) (Co(II)TPP: cobalt (II) tetraphenylporphyrin; Cr(PhH)(2): bis(benzene)chromium; o-C(6)H(4)Cl(2): o-dichlorobenzene) containing CoTPP(C(60)(CN)(2)- anion and C(60)(CN)(2).- radical anion was obtained. The complex has the cage structure with channels, which accommodate Cr(I)(PhH)(2)(.+) and o-C(6)H(4)Cl(2) molecules. For the first time the sigma-bonding of Co(II)TPP to the fullerene radical anion with the essentially shortened Co.C(C(60)(CN)(2)) contact of 2.282 A is observed. The sigma-bonding results in the diamagnetism of Co(II)TPP(C(60)(CN)(2))(-) anion. The nonbonded C(60)(CN)(2)(.-) radical anion retains both the C(2)(v)symmetry and the shape of the molecule. The length of the C(triple bond)N bonds is 1.141 and 1.152 A.     

Anion-directed crystallization of coordination polymers: syntheses and characterization of Cu(4)(2-pzc)(4)(H(2)O)(8)(Mo(8)O(26)).2H(2)O and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2-pzc = 2-pyrazinecarboxylate)

Two new copper 2-pyrazinecarboxylate (2-pzc) coordination polymers incorporating [Mo(8)O(26)](4-) and [V(10)O(28)H(4)](2-) anions were synthesized and structurally characterized: Cu(4)(2-pzc)(4))(H(2)O)(8)(Mo(8)O(26)).2H(2)O (1) and Cu(3)(2-pzc)(4)(H(2)O)(2)(V(10)O(28)H(4)).6.5H(2)O (2). Crystal data: 1, monoclinic, space group P2(1)/n, a = 11.1547(5) A, b = 13.4149(6) A, c = 15.9633(7) A, beta = 90.816(1) degrees; 2, triclinic, space group P1, a = 10.5896(10) A, b = 10.7921(10) A, c = 13.5168(13) A, alpha = 104.689(2) degrees, beta = 99.103(2) degrees, gamma = 113.419(2) degrees. Compound 1 contains [Cu(2-pzc)(H(2)O)(2)] chains charge-balanced by [Mo(8)O(26)](4-) anions. In compound 2, layers of [Cu(3)(2-pzc)(4)(H(2)O)(2)] form cavities that are filled with [V(10)O(28)H(4)](2-) anions. The magnetic properties of both compounds are described.     

一维锰金属配位化合物[Mn(oba)(L)(H_2O)]·2H_2O的合成和晶体结构

以六水合氯化锰,二苯甲醚二羧酸(Hoba)和吡嗪[2,3-f]邻菲咯啉(L)为原料合成了一种新型化合物[二水合(二苯甲醚二羧酸)(吡嗪[2,3-f]邻菲咯啉)水合锰][Mn(oba)(L)(H2O)].2H2O(1),该化合物为链状结构,吡嗪[2,3-f]邻菲咯啉(L)配体间的π-π相互作用将化合物连接成二维超分子结构.