Two heptacopper(II) disk complexes with a [Cu(7)(μ(3)-OH)(4)(μ-OR)(2)](8+) core

The reaction of CuX(2) (X(-) ≠ F(-)) salts with 1 equiv of 3-pyridyl-5-tert-butylpyrazole (HL) in basic methanol yields blue solids, from which disk complexes of the type [Cu(7)(μ(3)-OH)(4)(μ-OR)(2)(μ-L)(6)](2+) and/or the cubane [Cu(4)(μ(3)-OH)(4)(HL)(4)](4+) can be isolated by recrystallization under the appropriate conditions. Two of the disk complexes have been prepared in crystalline form: [Cu(7)(μ(3)-OH)(4)(μ-OCH(2)CF(3))(2)(μ-L)(6)][BF(4)](2) (2) and [Cu(7)(μ(3)-OH)(4)(μ-OCH(3))(2)(μ-L)(6)]Cl(2)·xCH(2)Cl(2) (3·xCH(2)Cl(2)). The molecular structures of both compounds as solvated crystals can be described as [Cu?Cu(6)(μ-OH)(4)(μ-OR)(2)(μ-L)(6)](2+) (R = CH(2)CF(3) or CH(3)) adducts. The [Cu(6)(μ-OH)(4)(μ-OR)(2)(μ-L)(6)] ring is constructed of six square-pyramidal Cu ions, linked by 1,2-pyrazolido bridges from the L(-) ligands and by basal, apical-bridging hydroxy or alkoxy groups, while the central Cu ion is bound to the four metallamacrocyclic hydroxy donors in a near-regular square-planar geometry. The L(-) ligands project above and below the metal ion core, forming two bowl-shaped cavities that are fully (R = CH(2)CF(3)) or partially (R = CH(3)) occupied by the alkoxy R substituents. Variable-temperature magnetic susceptibility measurements on 2 demonstrated antiferromagnetic interactions between the Cu ions, yielding a spin-frustrated S = (1)/(2) magnetic ground state that is fully populated below around 15 K. Electrospray ionization mass spectrometry, UV/vis/near-IR, and electron paramagnetic resonance measurements imply that the heptacopper(II) disk motif is robust in organic solvents.     

Reversible Solvatomagnetic Effect in Novel Tetranuclear Cubane-Type Ni(4) Complexes and Magnetostructural Correlations for the [Ni(4)(μ(3)-O)(4)] Core

A new family of tetranuclear nickel cube complexes [Ni(4)L(4)(solv)(4)] (1, solv = MeOH; 2, solv = H(2)O; H(2)L = pyrazole-based tridentate {ONO} ligand) has been studied in detail, in particular by X-ray diffraction and superconducting quantum interference device (SQUID) magnetometry. Different solvates 1·H(2)O, 2·4C(3)H(6)O, 2·CH(2)Cl(2), and 2·H(2)O were obtained in crystalline form. Only small structural variations were found for the Ni-O-Ni angles of the [Ni(4)O(4)] cores of those compounds, but these slight variations have dramatic consequences for the magnetic properties. [Ni(4)L(4)(MeOH)(4)]·H(2)O (1·H(2)O) and [Ni(4)L(4)(H(2)O)(4)]·H(2)O (2·H(2)O) can be reversibly interconverted in the solid state by exposure to the respective solvent, MeOH or H(2)O, and this goes along with a switching of the spin ground state from magnetic (S(T) = 4) to diamagnetic (S(T) = 0). Likewise the (irreversible) loss of lattice solvent in [Ni(4)L(4)(H(2)O)(4)]·4C(3)H(6)O (2·4C(3)H(6)O) to give 2·2C(3)H(6)O changes the ground state from S(T) = 4 to S(T) = 0. In view of these dramatic solvatomagnetic effects for the present [Ni(4)L(4)(solv)(4)] complexes, which occur upon extrusion of lattice solvent or facile exchange of coordinated solvent molecules while keeping the robust [Ni(4)O(4)] core intact, a note of care is issued: whenever magnetic data are obtained for powdered material or for crystals that easily loose lattice solvent molecules, the magnetic properties may not necessarily reflect the situation observed in the corresponding single crystal diffraction study. Finally, a thorough analysis of the present series of complexes as well as other {Ni(4)(μ(3)-OR)(4)} cubes reported in the literature confirms that a correlation between the (Ni-O-Ni)(av) bond angle and J in [Ni(4)O(4)] cubane complexes does indeed exist.     

[Cu(L-Ile)(Phen)(H2O)(ClO4)]的合成、结构及稳定性研究

合成了三元混配配合物[Cu(L-Ile)(Phen)(H20)(ClO4)](L-Ile=L-异亮氨酸,phen=1,10-邻菲咯啉),通过红外光谱、紫外-可见光谱、摩尔电导率、X射线单晶结构分析,对配合物进行了表征.该晶体属单斜晶系,P21空间群,晶胞参数:a=1.1704(5)nm,b=0.8090(5)nm,c=2.1822(5)nm,β=98.061(5)°,Z=2,Dx=1.60Mg·m-3,R1=0.0462,wR2=0.1225.每个配合物分子中Cu(Ⅱ)离子与一个L-Ile(N,O)配体、一个Phen(N,N)配体、一个H2O(O)配体及一个ClO4-(O)形成六配位的畸变八面体构型.本文还用电位滴定法测定了配合物的稳定常数,结果表明,配合物具有高的稳定性.     

Zeolitic imidazolate framework [Zn(2)(IM)(4)·(DMF)] for UV-white light-emitting diodes

A polymorph of a [Zn(2)(IM)(4)·(DMF)] (IM: imidazolate; DMF: dimethyl formamide) framework was synthesized using a DMF template. The topology of a ZnN(4) framework is similar to that of zeolites with a chain of connected SiO(4) tetrahedra. This polymorph has a zeolite-like structure and a wave shape topology in the [010] direction. The main chain is connected to an imidazolate ligand. The structure has excellent chemical and thermal stability. This framework also exhibits broad range near-UV excitation from 350 nm to 430 nm and broadened photoluminescence emission at 445 nm. It has great potential as a phosphor in applications of near-UV or UV white light-emitting diodes.     

Tetramers Cu4(μ4-O)(η-X)6(L4): Analysis of structural data

This review summarizes structural parameters for forty five Cu₄(μ₄-O)(η-X)₆(L₄) tetramers. There are four types of structurally equal core units, CuCl₃ON, CuCl₃OO, CuCl₃OCl and CuBr₃ON. There are also tetramers which contain structurally unequal core units: CuCl₃ON (x2) and CuCl₂BrON (x2); CuCl₃ON (x1), CuCl₂BrON (x2) and CuCl₃OCl (x1). There is a tendency for an elongated Cu?Cu separation as well as Cu–L bond distances with increase of the covalent radius of the coordinating atom(s). Tetrahedral distortion around oxygen atom (OCu₄) increases in the order: 1.67° (CuCl₃OCl) < 2.10° (CuCl₃ON) < 2.11° (CuCl₃OO′) < 2.27° (CuBr₃ON). The mean Cu–Cl–Cu bridge angle of 80.5° is about 4.0° more open than that of a Cu–Br–Cu (76.5°). The cluster Cu₁₆O₄Br₇Cl₁₇(4-Mepy)₁₆ (4-Mepy = 4-methylpyridine) contains four crystallographically independent tetramers: Cu₄OBrCl₅(4-Mepy)₄ (1), Cu₄OBrCl₅(4-Mepy)₄ (2) Cu₄OBr₂Cl₄(4-Mepy)₄ (3) and Cu₄OBr₃Cl₃(4-Mepy)₄ (4), which is a unique example of stereoisomerism. There are other examples which exist in two isomeric forms. Another contains two or even four crystallographically independent tetramers within the same crystal, differing mostly by degree of distortion and is an examples of distortion isomerism. Pairs of Cu₄OCl₆(n-Meim)₄ (n-Meim = n-methylimidazole) (n = 1 or 2) are examples of ligand isomerism.     

Vibrational spectroscopy of the multi-anion mineral zykaite Fe4(AsO4)(SO4)(OH)·15H2O-implications for arsenate removal

Some minerals are colloidal and are poorly diffracting. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of minerals. Among this group of minerals is zykaite with formula Fe(4)(AsO(4))(SO(4))(OH)·15H(2)O. The objective of this research is to determine the molecular structure of the mineral zykaite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching vibrations. The sharp band at 3515 cm(-1) is assigned to the stretching vibration of the OH units. This mineral offers a mechanism for the formation of more crystalline minerals such as scorodite and bukovskyite. Arsenate ions can be removed from aqueous systems through the addition of ferric compounds such as ferric chloride. This results in the formation of minerals such as zykaite and pitticite (Fe(3+), AsO(4), SO(4), H(2)O).     

[Cr(III)(4-ASA)(en)2]Cl配合物的光化学活性

通过吸收光谱、荧光光谱、电导率和ESI-MS质谱等方法讨论了铬配合物[Cr(III)(4-ASA)(en)2]Cl (4-ASA: 4-aminosalicylic acid dianion, en: ethylenediamine)在不同温度、不同pH溶液中的稳定性及光化学稳定性. 实验表明, 该配合物的溶液(pH 7.4)在日光照射下发生了光化学取代反应, 取代产物为[Cr(4-ASA)(en)(H2O)2]＋. 同时研究了配合物及其光照产物对EDTA的动力学反应和对DNA的切割反应. 琼脂糖凝胶电泳实验表明, 配合物的光化学产物[Cr(4-ASA)(en)(H2O)2]＋能有效切割pBR 322 DNA.     

{[Co(4，4′-bipy)(ambdc)(H2O)2](4，4′-bipy)(DMF)}n合成与晶体结构

A novel coordination polymer of {[Co(4,4′-bipy)(ambdc)(H₂O)₂](4,4′-bipy)(DMF)}_n has been synthesized using 5-aminoisophthalic acid (H₂ambdc), 4,4′-bipyridine(4,4′-bipy) and metal salts. The ambdc ligand in title compound has a μ₂-monodentate coordination mode and the structure of the title compound is a two-dimensional network. CCDC: 279054.     

Dangling thiyl radical: stabilized in [PPh4]2[(bdt)W(VI)(O)(μ-S)2Cu(I)(SC6H4S•)

The synthesis, crystal structure, and spectroscopic characterization of [PPh(4)](2)[(bdt)W(O)(S(2))Cu(SC(6)H(4)S(?))] (3; bdt = benzenedithiolate) relevant to the active site of carbon monoxide dehydrogenase are presented. Curiously, in 3, the copper(I) benzenemonothiolate subcenter possesses a dangling thiyl radical that is stabilized by a disulfido-bridged oxo tungsten dithiolene core. The benzenedithiolate ligand, which is generally bidentate in nature, acts as a bidentate and also as a monodentate in 3. The formation of an unusual dangling thiyl radical has been magnetically and spectroscopically identified and has been supported by the density functional theory level of calculation.     

STRUCTURE OF [W(H)_2(F)(OH_2)(PMe_2)_4]F

<正> Mr = 546.3, orthorhombic, space group Cmc21, a = 14.223(4), b = 12.907(3), c = 12.343(4) A, V = 2265.746 A3, Z = 4, DC = 1.601 Mg.m-3, λ= 0.7106 A, μ(MoK(?)) = 56.86 cm-1, F(OOO) = 1048. Final R = 0.044 for 1937 observed reflections. Cation [W(H)2(F)(OH2)(PMes)4]4 has a mirror symmetry, an equatorial belt of four PMe3 groups and mutually syn fluoride and water Ugands. The mean W-P length is 2.462 (A) and P-C 1.83 (A). From the dimensions of the metal, fluoride and water system ( W(1)-F(1) = 2.08(1), W(1)-0(1) - 2.084(9), F(2)-O(1) = 2.59(2) A and F(2)-W(1)-O(1) - 76.7(4)°) an in-terligand hydrogen bond was assumed. The ligand water molecule also makes an H-bonded contact with the fluoride counter ion.     

X-ray structure of (N-heterocyclic)(η4-diene)-dicarbonyliron(0) compounds

(N-Heterocyclic)(η⁴-diene)dicarbonyliron(0) compounds, where the N-heterocycles are quinoline and pyrazine and the diene is the diethyl ester of the hexa-2,4-dien-1,6-dioic acid (diethyl muconate) were studied by X-ray diffraction. The measurements demonstrated that the N-heterocycle occupies different positions of a tetragonal pyramid in these compounds. Quinoline occupies a basal position and pyrazine an apical position. This is discussed in terms of the π-bonding ability of the ligands.     

Synthesis of 62-electron square planar clusters with group 15 and 16 main group atoms: Structural characterization of Ru4(CO)11(μ4-PPh)(μ4-S) and Ru4(CO)10(μ4-PPh)(μ4-Se)(PEt3): Bonding preferences in cappingNido Ru4(CO)13(μ3-PPh)

Thecloso octahedral cluster Ru₄(CO)₁₁(μ₄-PPh)(μ₄-S)1 and selenium and tellurium analogues, the first examples of unsaturated ruthenium clusters with a planar metal core and different main group 15 and 16 atoms have been synthesized fromnido Ru₄(CO)₁₃(μ₃-PPh). An X-ray analysis of1 and Ru₄(CO)₁₀(μ₄-PPh)(μ₄-Se)(PEt₃)2a has confirmed thetrans disposition of phosphorus and group 16 main group fragments.     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

Synthesis and Crystal structure of Poly{[Co(4,4''''-bpy)(H_2O)_4]SO_(4·)(4-abaH)_(2·)3H_2O}

1 INTRODUCTION The researches on 4,4?-bpy bridged transition me-tal coordination polymers (4,4?-bpy = 4,4?-bipyri-dine) assembled through covalent or hydrogen bondshave attracted great interest in the past decade due toits structural diversities and potential applications[1～5].So far a number of one-, two- and three-dimensio-nal coordination polymers containing N,N?-bidentatespacers with infinite chain[6, , diamond[4], rectangle[8～11], 7]T-shape[5, 12], ladder[13～15], octahedron[16] an…     

A structural and Mössbauer study of complexes with Fe(2)(micro-O(H))(2) cores: stepwise oxidation from Fe(II)(micro-OH)(2)Fe(II) through Fe(II)(micro-OH)(2)Fe(III) to Fe(III)(micro-O)(micro-OH)Fe(III)

Dinuclear non-heme iron clusters containing oxo, hydroxo, or carboxylato bridges are found in a number of enzymes involved in O(2) metabolism such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases. Efforts to model structural and/or functional features of the protein-bound clusters have prompted the preparation and study of complexes that contain Fe(micro-O(H))(2)Fe cores. Here we report the structures and spectroscopic properties of a family of diiron complexes with the same tetradentate N4 ligand in one ligand topology, namely [(alpha-BPMCN)(2)Fe(II)(2)(micro-OH)(2)](CF(3)SO(3))(2) (1), [(alpha-BPMCN)(2)Fe(II)Fe(III)(micro-OH)(2)](CF(3)SO(3))(3) (2), and [(alpha-BPMCN)(2)Fe(III)(2)(micro-O)(micro-OH)](CF(3)SO(3))(3) (3) (BPMCN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane). Stepwise one-electron oxidations of 1 to 2 and then to 3 demonstrate the versatility of the Fe(micro-O(H))(2)Fe diamond core to support a number of oxidation states with little structural rearrangement. Insight into the electronic structure of 1, 2', and 3 has been obtained from a detailed M?ssbauer investigation (2' differs from 2 in having a different complement of counterions). Mixed-valence complex 2' is ferromagnetically coupled, with J = -15 +/- 5 cm(-)(1) (H = JS(1).S(2)). For the S = (9)/(2) ground multiplet we have determined the zero-field splitting parameter, D(9/2) = -1.5 +/- 0.1 cm(-)(1), and the hyperfine parameters of the ferric and ferrous sites. For T < 12 K, the S = (9)/(2) multiplet has uncommon relaxation behavior. Thus, M(S) = -(9)/(2) <--> M(S) = +(9)/(2) ground state transition is slow while deltaM(S) = +/-1 transitions between equally signed M(S) levels are fast on the time scale of M?ssbauer spectroscopy. Below 100 K, complex 2' is trapped in the Fe(1)(III)Fe(2)(II) ground state; above this temperature, it exhibits thermally assisted electron hopping into the state Fe(1)(II)Fe(2)(III). The temperature dependence of the isomer shifts was corrected for second-order Doppler shift, obtained from the study of diferrous 1. The resultant true shifts were analyzed in a two-state hopping model. The diferric complex 3 is antiferromagnetically coupled with J = 90 +/- 15 cm(-)(1), estimated from a variable-temperature M?ssbauer analysis.     

网状结构[NH4]2·[In(OH)(PO4)(H2O)]2的离子热合成与表征

以尿素与氯化胆碱为原料制备的低共熔点离子液体为反应介质,在离子热体系下制备了[NH4]2·[In(OH)(PO4)(H2O)]2,单晶结构分析表明晶体空间群为P41212,a=b=9·4309(4),c=11·1173(10),α=β=γ=90°,Z=4,V=988·79(11)~3,R1=0·0767,wR2=0·2027。晶体结构中In与P分别采用八面体与四面体配位。八面体与四面体通过顶角O原子连接,形成4,6-net网状结构。晶体在300℃下几乎没有失重。     

CRYSTAL STRUCTURE OF (Br(μ-Met)(μ-Gly)(H_2O)_4]_2[Er(μ-Net)_2(H_2O)_4]_2(ClO_4)_(12)

<正> [Er(u-Met)(u-Gly)(H2O)4]2[Er(u-Met)2(HaO)4]2(ClO4)12(NMet=CH3S-(CH2)2CH(NH2)COOH,Gly=NH2CH2COOH), Mr=3194, trilinic, space group P1, a = 12.375(6),b= 14.041(13), c=19.074(13)A,α=80.85(6),β=80.72(6).γ=62.82(6)° ,Z=1,V= 2896A3,Dc=1.83 g/cm3,R=0.091. The carboxyl groups of Met and Gly in the title complex are bonded to Er atoms as bidentate bridging ligands.There are two different cations located at crystallographic symmetry centers in one unit cell.     

Alkylimido osmium(VI) and ruthenium(VI) porphyrins. Crystal and molecular structures of Os(TTP)(O)(NBu~t)·EtOH and Os(4-Cl-TPP)(NBu~t)_2

Oxo(tert-butylimido) or bis(tert-butylimido)osmium(VI) porphyrins Os(Por)(O)(NBut) and Os(Por)(NBut)2, [Por=meso-tetrakis(p-tolyl)porphyrinato (TTP) and meso-tetrakis(4-chlorophe-nyl)porphyrinato (4-Cl-TPP)] were synthesized by air oxidation of bis(tert-butylamme)osmium(II) porphyrins [Os(Por)(H2NBut)2 (Por=TPP, 4-Cl-TPP], depending on whether tert-butylamine is present. The bis(tert-butylamine)ruthenium(II) porphyrins [Ru(Por)(H2NBut)2, Por=TTP, 4-Cl-TPP] can undergo bromine oxidation to give oxo(tert-butylimido)ruthenium(VI) complexes in quantitative yields. All these new complexes were characterized by 1H NMR, UV-Visible and IR spectroscopy. The X-ray crystal structures of Os(TTP)(O)(NBut).EtOH and Os(4-Cl-TPP)(NBut)2 have been determined. Crystal data: for Os(TTP)(O)(NBut).EtOH: monoclinic, space group P21/c, a=1.3546(6) nm, b=2.3180(3) nm, c=1.6817(3) nm, B=90.84(2), V=527.97(1) nm3, Z=4. The Os=O and Os=NBut distances in Os(TTP)(O)(NBut).EtOH are 0.1772(7) nm and 0.1759(9) nm, respectively. The av     

A vibrational spectroscopic study of the mixed anion mineral sanjuanite Al2(PO4)(SO4)(OH)·9H2O

The mineral sanjuanite Al2(PO4)(SO4)(OH)·9H2O has been characterised by Raman spectroscopy complimented by infrared spectroscopy. The mineral is characterised by an intense Raman band at 984 cm(-1), assigned to the (PO4)3- ν1 symmetric stretching mode. A shoulder band at 1037 cm(-1) is attributed to the (SO4)2- ν1 symmetric stretching mode. Two Raman bands observed at 1102 and 1148 cm(-1) are assigned to (PO4)3- and (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence for the reduction in symmetry of both anions. This concept is supported by the multiple sulphate and phosphate bending modes. Raman spectroscopy shows that there are more than one non-equivalent water molecules in the sanjuanite structure. There is evidence that structural disorder exists, shown by the complex set of overlapping bands in the Raman and infrared spectra. At least two types of water are identified with different hydrogen bond strengths. The involvement of water in the sanjuanite structure is essential for the mineral stability.     

Synthesis and study of the properties of the solid solutions K2Y1−x Tb(Tm) x (MoO4)(PO4) and K2Y1−x Tm x (MoO4)(PO4)0.95(VO4)0.05

The solid solutions K₂Y_1?x Tb(Tm) _x (MoO₄)(PO₄) and K₂Y_1?x Tm _x (MoO₄)(PO₄)_0.95(VO₄)_0.05 were synthesized, which are isostructural and crystallize in the orthorhombic crystal system (space group Ibca). The luminescence intensity of the terbium-containing samples increases with increase in the terbium content. The thulium-containing samples are characterized by intense luminescence in the blue spectral region and concentration quenching of luminescence. The introduction of the vanadate anion adversely affects the luminescence intensity.