{[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.     

[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.     

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.     

[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.     

Dimeric uranium complexes with bridging phospholyl ligands. Crystal structure of [{U(η5-C4Me4P)(μ-η5-C4Me4P)(BH4)}2]

In the symmetrical crystal structure of [{U(η⁵-C₄Me₄P)(μ-η⁵,η¹-C₄Me₄P)(BH₄)}₂], the U-P bond distances for the terminal and bridging η⁵-phospholyl ligands are 2.945(3) and 2.995(3) Å respectively, and the U-P (η¹-phospholyl) bond length is equal to 2.996(3) Å; the tridentate borohydride ligands are cis to the (UP)₂ ring. The cis and trans isomers of [{U(Cp¹)(μ-η⁵,η¹C₄ Me₄P)(BH₄)}₂] (Cp¹ = η⁵-C₅Me₅) are in equilibrium in toluene.     

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.     

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。     

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.     

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.     

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.     

二维配合物[Cd(mpac)(4，4-bpy)(OH)]n的合成，晶体结构和荧光性质

溶剂热条件下采用Cd(NO3)2.4H2O,5-甲基吡嗪-2-甲酸和4,4-联吡啶作为反应物合成出一个新的具有二维层状结构的镉金属配位聚合物[Cd(mpac)(4,4-bpy)(OH)]n(1),并分别用元素分析,红外光谱,热重分析和X-射线单晶衍射表征该结构。晶体结构分析结果表明:5-甲基吡嗪-2-甲酸将Cd(Ⅱ)离子连接成一维链,这些链进一步被4,4-联吡啶连接成二维层状结构。在二维层状结构中存在大小为0.24×1.16 nm2的一维通道。荧光谱图表明常温固态下配合物1发射蓝色荧光。     

[Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)]·2H~2O的合成和晶 体结构

将适量邻菲啰啉、丁二酸和CuCl~2·2H~2o(摩尔比=1:1)溶于水和甲醇的混合溶剂[V(水):V(甲醇)=1:1]后,滴加NaOH溶液至pH=4.8。滤去沉淀物后,滤液于室温下缓慢蒸发得蓝色细长[Cu(C~1~2H~8N~2)(H~2O)(C~4H~4O~4)]·2H~2O晶体。晶体属三斜晶系,P1(No.2)空间群。晶胞参数a=0.7462(1)nm,b=(0.9959)1nm,c=1.2266(1)nm,α=75.02(1)°,β=82.38(1)°,γ=74.76(1)°,V=0.8475(2)nm^3,Z=2,D~c=1.622g·cm^3,F(000)=426.3882个独立衍射点中,2789个可观测点满足F~0^2≥2σ(F~0^2),R=0.0450,wR^2=0.0951。配合物内每个Cu与邻菲啰啉螯合配体中的2个N原子、来自不同羧酸根的2个羧基O和1个水分子O原子配位,形成扭曲的四方锥体,其中一羧基O位于锥顶[d(Cu－N)=0.2006(3),0.2032(3)nm;赤道d(Cu－O)=0.1972(2),0.1973(2)nm;轴向d(Cu－O)=0.2210(2)nm]。双齿桥联丁二酸根连接Cu原子形成平行于[100]方向的多聚超分子链^1~∞[Cu(phen)~2(H~2O)·(C~4H~4O~4)~2~/~2]~2。芳环堆积间距交替为0.366nm和0.380nm。未配位的H~2O分子位于超分子双链之间。     

A 2-D Copper Coordination Polymer [Cu(4,4''''-bpy)(H_2O)_4](C_4H_2O_4)(H_2O)_4 Integrated by Hydrogen Bonds and VDW Interactions

1 INTRODUCTION A great deal of interest in transition metal com- plex assembly has recently been devoted to the development of rational synthetic routes to novel one-, two- and three-dimensional crystal frameworks, due to their potential applications in…     

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.     

The synthesis,structure and reactions of the novel cationic bisbut-2-yne complex [W(CO)(NCMe)(S2CNC4H8)(η2-MeC2Me)2][BPh4]

The complex [WI(CO)(S₂CNC₄H₈)(η²-MeC₂Me)₂] reacts with an equimolar amount of Na[BPh₄] in acetonitrile at room temperature to give the cationic bisbut-2-yne complex [W(CO)(NCMe)(S₂CNC₄H₈)(η²-MeC₂Me)₂][BPh₄] (1) by replacement of an iodide ligand by acetonitrile. The crystal structure of 1 has been determined and reveals a pseudo-octahedral geometry with the mid points of the two cis-but-2-yne ligands approximately coplanar with the sulphur atoms of the dithiocarbamate ligand. Carbon monoxide and acetonitrile occupy the axial sites. ¹³C NMR spectroscopy shows the two but-2-yne ligands in 1 donate a total of 6 electrons to the tungsten. Preliminary studies of the chemistry of 1 are also described.     

Generation of the dichloromethane complex [(η5-C5Me5)Re(NO)(PPh3)(ClCH2Cl]+ BF4−, and its conversion to the oxidative addition product [(η5-C5Me5)Re(NO)(PPh3)(Cl)(CH2Cl)]+ BF4−

Reaction of (η⁵-C₅Me₅)Re(NO)(PPh₃)(CH₃) and HBF₄ · OEt₂ in CH₂Cl₂ at −78°C gives the dichloromethane complex [η⁵-C₅Me₅Re(NO)(PPh₃)(ClCH₂Cl)]⁺ BF₄⁻, which undergoes the title transformation at −35°C. The ReClCH₂Cl carbon is attacked by halide nucleophiles (X⁻) to give XCH₂Cl and the chloride complex (η⁵-C₅Me₅)Re(NO)(PPh₃)(Cl), and exhibits a ¹³C NMR resonance that is coupled to phosphorus (d, ³J(CP) 5.0 Hz) and geminal hydrogens (t, ¹J(CH) 186 Hz).     

Nitrile-rich coordination polymer (1)(∞){[Fe(CH(3)CN)(4)(pyrazine)](ClO(4))(2)} exhibiting a HS ⇆ LS transition

In a 1D network of (1)(∞){[Fe(CH(3)CN)(4)(pyrazine)](ClO(4))(2)}, the presence of four neutral nitrile molecules besides the pyrazine donors in the first coordination sphere of iron(II) allows one to achieve a ligand field strength appropriate for the "spin-crossover" occurrence.     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

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.