配合物Zn(TC-TTF)0.5(bipy)2(CH3OH)的合成与结构表征

在有机导体和超导体领域,四硫富瓦烯(TTF)及其衍生物受到研究者广泛的关注[1,2].由于TTF电荷转移金属配合物具有特殊的结构和性质,它们不仅可以作为分子导体的构成部分,而且可以作为非线性光学材料、传感器、液晶材料以及薄膜材料的构筑模块,在材料化学等诸多领域显示出广阔的应用前景[3～5].     

Electron microscopy and structural studies of Nd1/3NbO3

The crystal structure of the deficient perovskite Nd_1/3NbO₃ has been determined at room temperature, using electron microscopy observations and X-ray powder diffraction data. Electron diffraction study and HRTEM images evidence the doubling of a and b parameters and confirm one of the c-parameter with respect to perovskite unit cell. The structure refinement has been carried out using the orthorhombic Cmmm space group. The Nd³⁺ cations occupy randomly and alternatively the (00l) planes and Nb⁵⁺ cations distorted octahedral sites. This structure is characterized by the presence of empty Nd³⁺ sites in every second layer and the tilting of the octahedral sites around the b-axis. In addition, electron diffraction patterns exhibit weak additional diffuse reflections, which supposes some ordering of the Nd vacancies.     

Synthesis and reactivity of new heterodinuclear iron/rhenium Cx complexes of the formula (η-C5Me5)Re(NO)(PPh3)(CC)n(η-dppe)Fe(η-C5Me5) (n = 3, 4): Redox properties and a dicobalt hexacarbonyl adduct

We report in this communication the synthesis and characterization of two Fe/Re heterodinuclear complexes 3_n of formula (η⁵-C₅Me₅)Re(NO)(PPh₃)(CC)_n(η²-dppe)Fe(η⁵-C₅Me₅) (n = 3, 4) as well as the hexacarbonyl dicobalt adduct (4) of the hexatriynediyl complex 3₃. We show by cyclic voltammetry that the “electronic communication” between the organometallic endgroups and thereby the thermodynamic stability of the corresponding mixed-valent (MV) parent 3_n⁺ is strongly influenced by bridge extension or by complexation of the [Co₂(CO)₆] fragment. In the case of the hexatriynediyl complex, the MV complex 3₃⁺ or 4 can be isolated by performing the chemical oxidation of 3₃ at low temperature. Spectroscopic studies of this compound and of other stable oxidized redox congeners should now help us to unravel how bridge extension modifies the electronic communication between the different redox-active endgroups in this family of unsymmetrically-substituted polyynediyl compounds.     

Vibrational spectra of α-Ge(HPO4)2·H2O compound

We have measured Raman and infrared spectra of α-Ge(HPO₄)₂·H₂O compound at room temperature. The analysis of vibrational modes indicated the presence of two non-equivalent HPO₄²⁻ units in agreement with ³¹P nuclear magnetic resonance measurements. A tentative assignment of all the observed modes is proposed based on the previous works reported for other hydrogenphosphate-based compounds.     

Synthesis, crystal structures and magnetic properties of 2,3,6,7-tetrakis(2-cyanoethylthio)tetrathiafulvalene salts

The synthesis of the protected TTF tetrathiolate 2,3,6,7-tetrakis(2-cyanoethylthio)tetrathiafulvalene (TCE-TTF), as well as those of five new radical cation salts [TCE-TTF](X), X⁻ = PF₆⁻, CF₃SO₃⁻, BF₄⁻, obtained by electrocrystallization technique is presented. Five crystal structures of these materials based on their fully oxidized donor molecules are described. The flexibility of the cyanoethylene arm yields two conformations cis and trans to the molecule. Then compounds with PF₆⁻ and BF₄⁻ anions crystallized as two different phases. All these materials are insulators, and the magnetic studies of one phase of [TCE-TTF](PF₆) revealed an antiferromagnetic behavior.     

Novel M(II)–Hg(II) coordination polymers generated from metal-containing building blocks M(2-pyrazinecarboxylate)2 · (H2O)2 (M=Cu, Ni, Co) and HgCl2

A new class of M(II)–Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate)₂HgCl₂ (4), [Co(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.61H₂O (5) and [Ni(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.77H₂O (6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂(M=Cu(II), Co(II), Ni(II)), with HgCl₂. Compounds 4–6 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) ų, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)–Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P , with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) ų, Z=1. Compound 6 also crystallized in the triclinic space group P , with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) ų, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)M(II)Hg(II) units are connected by Hg₂Cl₂ linkages to produce a novel M(II)–Hg(II) (M=Co(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M–M′–M′–M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂ (M=Cu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl₂ depending on the metal cation contained within them.     

IR and Raman spectra of two layered aluminium phosphates Co(en)3Al3P4O16 · 3H2O and [NH4]3[Co(NH3)6]3[Al2(PO4)4]2 · 2H2O

The FT IR and FT Raman spectra of Co(en)₃Al₃P₄O₁₆ · 3H₂O (compound I) and [NH₄]₃[Co(NH₃)₆]₃[Al₂(PO₄)₄]₂ · 2H₂O (compound II) are recorded and analysed based on the vibrations of Co(en)₃³⁺, Co(NH₃)₆³⁺, NH₄⁺, Al---O---P, PO₃, PO₂ and H₂O. The observed splitting of bands indicate that the site symmetry and correlation field effects are appreciable in both the compounds. In compound I, the overtone of CH₂ deformation Fermi resonates with its symmetric stretching vibration. The NH₄ ion in compound II is not free to rotate in the crystalline lattice. Hydrogen bonding of different groups is also discussed.     

Synthesis, crystal structure and magnetic properties of a novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O)

A novel complex [Cu(NIT2Py)(PDA)(H₂O)]·(CH₃OH)(H₂O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H₂O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H₂O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py.     

Unprecedented μ3-O face-capping ligand in a [Mo6Br6L2Br6] (L = 0.5 O + 0.5 Br) molybdenum cluster unit: crystal structure of the Cs3Mo6Br13O oxybromide

The new Cs₃Mo₆Br₁₃O oxybromide, synthesized by solid-state chemistry, crystallizes in the trigonal system (Rc space group; a = 15.5784(2) Å, c = 19.5103(5) Å, V = 4100.5(1) Å³ and Z = 6). It is based on a [Mo₆L₁₄] unit that contains an unprecedented μ₃ face-capping oxygen. The crystal structure determined by single crystal X-ray diffraction is built up from discrete face-capped [Mo₆Brⁱ₆Lⁱ₂Br^a₆]^3– (L = 0.5 O + 0.5 Br) anionic units in which two inner positions are randomly occupied by one bromine and one oxygen whereas the other ligand positions are fully occupied by bromine. The cesium cations randomly occupy two close crystallographic positions generated by the A-B-C-A′-B′-C′ close-packed stacking of the units. The cesium site occupancy is related to the random distribution of oxygen and bromine on the Lⁱ inner positions. To cite this article: K. Kirakci et al., C. R. Chimie 8 (2005).     

{XW12O40 [Cu(en)2(H2O)]3} (X=V, Si): Two novel tri-supported Keggin POMs with transition metal complexes

Two novel polyoxometalate derivatives, {X^IVW^VI₁₀W^V₂O₄₀[Cu(en)₂(H₂O)]₃} [X=V (1), Si (2); en=ethylenediamine], have been hydrothermally synthesized and characterized by elemental analyses, IR, UV–Vis, XPS, EPR, TG and single crystal X-ray diffraction analyses. They represent the first classical Keggin polyoxoanion supported by three transition metal complex moieties, which further act as the neutral molecular unit for the construction of the interesting three-dimensional supramolecular frameworks. The magnetic properties of 1 have also been studied in the temperature range of 4–300 K, and its magnetic susceptibility obeys the Curie–Weiss law, showing antiferromagnetic coupling.     

Studies on Mixed Monolayers and Langmuir–Blodgett Films of Schiff-Base Complex Cu(SBC18)2 and Calix[4]arene

Mixed monolayers of Schiff-base complex Cu(SBC₁₈)₂ with an octadecyl hydrocarbon chain and Calix[4]arene without a long alkyl chain at an air/water interface were studied in ultrapure water at different temperatures. Interface behavior and thermodynamic estimation of the mixed monolayer indicate that a strong intermolecular interaction exists between the mixed components (Cu(SBC₁₈)₂ and calix[4]arene) and the two-dimensional miscibility decreases with the molar fraction of Cu(SBC₁₈)₂. It is noticeable that the calix[4]arene monolayer can be transferred successfully onto solid substrates due to the introduction of Cu(SBC₁₈)₂. FTIR transmission and UV-Vis absorption spectra of mixed LB films provide further evidence of molecular interaction between the headgroups.     

Synthesis, crystal structure, infrared and Raman spectra of Sr4Cu3(AsO4)2(AsO3OH)4·3H2O and Ba2Cu4(AsO4)2(AsO3OH)3

The two new compounds, Sr₄Cu₃(AsO₄)₂(AsO₃OH)₄·3H₂O (1) and Ba₂Cu₄(AsO₄)₂(AsO₃OH)₃(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As₂O₅-H₂O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å³, Z=4 for 1; space group P4₂/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å³, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu²⁺-(XO₄)³⁻ layers (X=P⁵⁺, As⁵⁺) linked by M cations (M=alkali, alkaline earth, Pb²⁺, or Ag⁺) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu₂O₈ centrosymmetric dimers crosslinked by As1φ₄ tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu₂O₈ centrosymmetric dimers of CuO₅ edge-sharing polyhedra, crosslinked by As1O₄ tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.     

两个具stp三维拓扑构型的稀土配位聚合物{[Ln_2(pda)_3(H_2O)_2]·2H_2O}_n(Ln=Nd,La)

本文利用水热合成方法,将稀土氧化物与邻苯二乙酸(H2pda)反应得到了2个新颖的稀土配位聚合物{[Ln2(pda)3(H2O)2]·2H2O}n(Ln=Nd(1),La(2))。测定了它们的晶体结构,并进行了X-射线单晶衍射、红外光谱、荧光光谱和热重分析等性质的表征。晶体结构测定表明这2个化合物为异质同晶化合物。属单斜晶系,C2/c空间群。晶体学参数分别为配合物1:a=2.629 06(18)nm,b=1.611 72(11)nm,c=0.783 27(5)nm,β=93.173(5)°,V=3.313 9(4)nm3,Z=4,F(000)=1 840,μ=3.173 mm-1,Dc=1.878 g·cm-3,R1=0.022 6,wR2=0.060 9;配合物2:a=2.627 1(14)nm,b=1.614 9(8)nm,c=0.796 6(4)nm,β=92.850(9)°,V=3.375(3)nm3,Z=4,F(000)=1 816,μ=2.570 mm-1,Dc=1.823 g·cm-3,R1=0.0466,wR2=0.1416。化合物中邻苯二乙酸配体连接相邻的稀土金属离子,形成复杂的具有stp拓朴构型的三维网络结构。     

A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: {[Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]}·2H3O·2H2O

A novel polyoxometalate {[Ni(enMe)₂]₂[Ni(enMe)₂(H₂O)]₂[As₂W₁₈Ni₄(enMe)₂O₆₈]}·2H₃O·2H₂O (1) (enMe = 1,2-propylenediamine) has been synthesized and characterized, which is the first high-dimensional structure constructed from sandwich-type transition metal substituted tungstates and transition metal coordination groups.     

An unexpected molybdenum(0) complex with “MoP6” coordination: crystal structure of [Mo{P(CH2CH2PPh2)3}2] · C5H10

The reaction of trans-[Mo(N₂)₂(PPh₂Me)₄] with the tripodal phosphine tris(2-diphenylphosphinoethyl)phosphine, PP₃, in benzene has been studied. The product was recrystallized from a mixture of benzene and petroleum ether to give [Mo(PP₃)₂]·C₅H₁₀, whose crystal structure shows a distorted octahedral “MoP₆” coordination with both phosphines acting as tridentate ligands.     

Solid substrate-room temperature phosphorimetry for the determination of trace protein using ion association complex [Cu(BPY)2]·[(Fin)2] as a phosphorescent probe

Fluorescein (HFin) emitted strong and stable room temperature phosphorescence (RTP) on filter paper after set at 50 °C for 10 min using Li⁺ as the ion perturber. HFin existed as Fin⁻ when the pH value was in the range of 5.45–7.36. Fin⁻ could react with [Cu(BPY)₂]²⁺ (BPY: α,α-bipyridyl) to produce ion association complex [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻, which could enhance the RTP signal of Hfin. In the presence of bovine serum albumin (BSA), the –COOH group of Fin⁻ in the [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻ could react with the –NH₂ group of BSA to form the ion association complex [Cu(BPY)₂]²⁺·[(Fin-BSA)₂]²⁻, which contained –CO–NH– bond. This complex could sharply enhance the RTP signal of Hfin and the ΔI_p was directly proportional to the content of BSA. According to the facts above, a new solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace protein had been established using the ion association complex [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻as a phosphorescent probe. This method had wide linear range (0.40 × 10⁻⁹–280 × 10⁻⁹ mg l⁻¹), high sensitivity (the detection limit (LD) was 1.4 × 10⁻¹⁰ mg l⁻¹), good precision (RSD: 3.4–4.9%) and high selectivity (the allowed concentration of coexistent ions or coexistent materials was high). It had been applied to the determination of the content of protein in 10 kinds of real samples, and the result agreed well with pyrocatechol violet-Mo (VI) method (P.V.M.M.), which indicated it had high accuracy. Meanwhile, reaction mechanism for the determination of trace protein with [Cu(BPY)₂]²⁺·[(Fin)₂]²⁻ phosphorescent probe was also discussed. The academic thought of this research could not only be used to develop many kinds of ion association complex phosphorescent probes, but also provided a new way to promote the sensitivity of SS-RTP.     

X-ray and multinuclear NMR study of the mixed aggregate [(Ph2P(O)N(CH2Ph)CH3) · LiOC6H2-2,6-{C(CH3)3}2-4-CH3) · C7H8]2: a model for the directed metalation of phosphinamides

The addition of LiBuⁿ to a toluene solution of Ph₂P(O)N(CH₂Ph)CH₃1 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph₂P(O)N(CH₂Ph)CH₃) · LiOC₆H₂-2,6-{C(CH₃)₃}₂-4-CH₃) · C₇H₈]₂6. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li₂O₂ core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (¹H, ⁷Li, ¹³C, ³¹P) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.     

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)2}2V4O12]·5H2O and [Ni(phen)3]2[V4O12]·17.5H2O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂]·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂]·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈O₂₂V₄ (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C₇₂H₁₃₁N₁₂Ni₂O_29.5V₄ (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]⁴⁻ cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]⁴⁻ cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]⁴⁻ cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]⁴⁻ unit and crystallization water molecules.     

Manganese(II) complexes of 3,6,9-trioxaundecanedioic acid (3,6,9-tddaH2): X-ray crystal structures of [Mn(3,6,9-tdda) (H2O)2]·2H2O and {[Mn(3,6,9-tdda)(phen)2·3H2O]·EtOH}n

3,6,9-trioxaundecanedioic acid (3,6,9-tddaH₂) reacts with Mn(CH₃CO₂)₂·4H₂O in ethanol to give [Mn(3,6,9-tdda)]·H₂O (1). Recrystallization of 1 from methanol gives crystals of [Mn(3,6,9-tdda) (H₂O)₂]·2H₂O (2). Complex 1 reacts with an ethanolic solution of 1,10-phenanthroline (phen) to give {[Mn(3,6,9-tdda)(phen)₂]·3H₂O·EtOH}_n (3). All of the complexes are extremely water soluble. Complexes 2 and 3 were structurally characterised. The manganese(II) ion in 2 is seven coordinate, with an approximately pentagonal bipyramidal O₇ coordination sphere. The axial donors are water molecules and the pentagonal plane is occupied by the diacid, acting as a pentadentate ligand through the three ethereal oxygens and one oxygen atom from each of the carboxylate functions. In complex 3 the manganese(II) ion is six-coordinate, being bound to two bidentate phenanthroline ligands and to the carboxylate oxygen atoms from two symmetry related diacids which are coordinated in a cis fashion. The structure consists of polymeric chains, with diacid ligands bridging the manganese ions. There is π-π stacking of pairs of phenanthroline ligands on adjacent chains, running along both the z and y directions.