A 2D polymer constructed through bridging oxalato and 4,4′-bipyridine ligands: crystal structure and magnetic behavior of [Cu3(μ-ox)3(μ-4,4′-bpy)2(4,4′-bpy)2]n

The crystal structure of the compound [Cu₃(μ-ox)₃(μ-4,4^′-bpy)₂(4,4^′-bpy)₂]_n 1 (ox=oxalato, 4,4^′-bpy=4,4^′-bipyridine) is comprised of two-dimensional sheets in which copper(II)–oxalato chains are cross-linked by bridging bidentate 4,4^′-bpy ligands. Metal centers show a tetragonally elongated octahedral environment formed by four oxygen atoms from two asymmetrically coordinated oxalato ligands and two nitrogen atoms from two trans-coordinated 4,4^′-bpy molecules. The magnetic measurements show the occurrence of weak ferromagnetic couplings.     

Synthesis,structure and properties of a new copper (II) complex, [Cu2(4,4′-bpy)5(H2O)4](ClO4)4(4,4′-bpy)(DMF)2(H2O)2

A new copper (II) complex with formula [Cu₂(4,4′-bpy)₅(H₂O)₄](ClO₄)₄(4,4′-bpy)(DMF)₂(H₂O)₂ has been synthesized by reaction of 4,4′-bpyridine (4,4′-bpy) with Cu(ClO₄)₂. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H?O bonds, anion?π and C–H?π interactions are also evident in the structure. The preliminary investigation on the thermal property of the complex is presented.     

Phosphorus–carbon bond cleavage of Ph2PCH2PPh2 at a triruthenium center: synthesis and structural characterization of [Ru3(μ-CO)(CO)6(μ-PPh2)2(μ3-CH2PPh)]

The reaction of Ph₂PH with [Ru₃(CO)₁₀(μ-dppm)] (1) at 98°C gave [Ru₃(μ-CO)(CO)₆(μ-PPh₂)₂(μ₃-CH₂PPh)] (7) in 20% yield. Compound 7 was characterized by elemental analysis, ¹H and ³¹P{¹H} NMR and mass spectroscopic data and also by a single crystal structure determination. The compound is shown to consist of a triruthenium cluster with an unusual example of a triply bridging CH₂PPh ligand and two doubly bridging PPh₂ ligands.     

Synthesis and crystal structure of a novel 2-D hybrid compound [(PbBr2)2(μ-Pyz)]n (Pyz=pyrazine)

A novel 2-D organic–inorganic hybrid compound [(PbBr₂)₂(μ-Pyz)]_n 1, has been prepared, and its X-ray structure shows that the supramolecular structure consists of organic–inorganic hybrid layers, each of which is constructed from two [PbBr₂]_n sheets and one pyrazine, via Pb–N bonding along the direction of the b-axis, and the divalent lead is penta-coordinated to form a hemidirected complex.     

Molecular assembly of novel hetero-metal clusters: [(O=MoS3Cu2)2(μ-Sn2S6)]4− and [(S=MoS3Cu2)3(μ3-S)2]4−

Two mixed molybdenum–copper–sulfur clusters containing two or three {E=MoS₃Cu₂} (E=O, S) fragments have been assembled around the nucleophiles μ₂-Sn₂S₆⁴⁻ or μ₃-S²⁻, viz. [(MoES₃Cu₂)₂(μ-Sn₂S₆)]⁴⁻ (E=0.7 O + 0.3 S) and [(MoS₄Cu₂)₃(μ₃-S)₂]⁴⁻.     

Synthesis,characterization and crystal structure of one Mn(II) complex with 4,4′-bisimidazolylbiphenyl and 4,4′-sulfonyldibenzoic acid

One new title compound [Mn₃(BIBP)(sdb)(NO₂⁻)₂(H₂O)₂]_n·2DMF (1) (BIBP = 4,4′-bisimidazolylbiphenyl, sdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling interaction.     

Synthesis,structure and calculated NLO properties of [(n-Bu)2Sn-μ-O-μ-OH-Sn(n-Bu)2(CH3CO2)]2 and its putative derivatives

Title compound[(n-Bu)₂Sn-μ-O-μ-OH-Sn(n-Bu)₂(CH₃CO₂)]₂ was obtained accidentally by the reaction of n-Bu₂SnCl₂ with the metalloligand K₂[Ni(CDC)₂] in ethanol - water mixture while synthesizing a heterobimetallic complex [n-Bu₂Sn Ni(CDC)₂]. This has been characterized by micro analysis, UV–Vis, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and the single crystal X-ray. The complex forms an interesting supramolecular architecture via (acetate)O?HO hydrogen bonding interactions which generates hydrophobic “pseudo-cage”. The electronic absorption bands of the title complex were assigned with the help of the time dependent density functional theory (TD-DFT) calculations. Density functional theory (DFT) calculations have been performed at the optimized molecular geometry of some of its putative derivatives e. g. trans p-amino cinnamic acid derivative 2; trans p-amino cinnamic acid and trans p-nitro cinnamic acid derivative 3; trans p-amino cinnamic acid and trans p-(N,N dimethylamino) cinnamic acid derivative 4. The first static hyperpolarizability (β) of the title compound and its derivatives were calculated with double numerical differentiation of total energies. The derivatives 3 and 4 showed three times and five times enhancement in the non-linear optical (NLO) responses than the standard p-nitroaniline (pNA).     

ZnCl3(4-methyl-4,4′-bipyridinium) with 4-methyl-4,4′-bipyridinium generated in situ: synthesis,structure and photoluminescence

A novel viologen(4,4′-bipyridinium)-based complex ZnCl₃(4-methyl-4,4′-bipyridinium) (1), in which the 4-methyl-4,4′-bipyridinium (MQ⁺) was generated in situ, has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. The title complex features an isolated structure, based on the MQ⁺ ligand coordinating to a zinc atom that is further terminally bound by three chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region, which may originate from π → π¹ charge-transfer interaction of the MQ⁺ ligand.     

Synthesis and structural characterization of [(μ-H)Ru3(CO)8{μ-S(CH2)3SH}(μ-dppe)] and [Ru3(CO)5{μ2-S(CH2)3S}2(η2-dppe)] (dppe=Ph2PCH2CH2PPh2)

The reaction of 1,3-propanedithiol with [Ru₃(CO)₁₀(μ-dppe)] (2) at 66°C afforded the thiolate complexes [(μ-H)Ru₃(CO)₈{μ-S(CH₂)₃SH}(μ-dppe)] (6) and [Ru₃(CO)₅{μ₂-S(CH₂)₃S}₂(η²-dppe)] (7) in 25 and 23% yields respectively. Compound 6 is formed by simple oxidative addition of one of the S–H bonds of 1,3-propanedithiol while the structurally unique 7 consists of an open triruthenium cluster with four terminal and one asymmetrically bridged carbonyl groups, two doubly bridged propanedithiolate ligands and a chelating dppe ligand.     

A photoluminescent metallophane [Cu2(μ-dppb)2(CH3CN)4](BF4)2 with a chair conformation: synthesis,structural and spectroscopic studies

A dinuclear copper(I) complex [Cu₂(μ-dppb)₂(CH₃CN)₄](BF₄)₂ (dppb=1,4-bis(diphenylphosphino)benzene) has been prepared and characterized by X-ray crystallography, absorption and luminescence spectrometry. The two copper atoms are double linked by two dppb ligands to form a metallophane with the two bridging phenyl rings parallel to each other. The core cyclophane-like structure adopts a chair conformation constructed by four coplanar P atoms and two phenyl rings from two dppb ligands, and the two copper atoms located above and below the mean plane. At room temperature, the complex in solid state exhibits photoluminescence originated from the intraligand excited state perturbed by copper coordination. The title complex may serve as a pre-organized dimetal building block for constructing novel supramolecular system.     

Synthesis and crystal structure characterization of Cu ( Ⅰ ) coordinational polymer {Cu(4,4'-bipy)Br}n

利用溶剂热法合成了标题化合物,其结构经元素分析和X-射线单晶衍射表征.标题化合物属于四方晶系,I41/acd空间群,晶胞参数:a=1.4443(4)、b=1.444 3(4)、c=3.855 0(15) nm、V=8.042(4) nm3、Z =32、Mr=299.63 g/mol、Dc=1.980 g·cm-3、μ =6.10 mm-1、F(000) =4 672、R1 =0.029、wR2=0.079、S=1.05.标题化合物中Cu+分别与两个4,4'-联吡啶上一个N原子配位以及两个端基溴原子配位,形成了四面体配位几何构型.分子内Cu…Cu之间的距离为0.282 95 (13) nm.在a+c轴方向,通过4,4’-联吡啶桥联作用形成二维层状网格,层与层通过互穿插形成三维结构.     

1D zigzag coordination polymer [Cu(tacn)(4,4′-bipy)]n·(ClO4)2n (tacn=1,4,7-triazacyclononane): structure,spectroscopic, and magnetic properties

A new one-dimensional coordination polymer, [Cu(tacn)(4,4^′-bipy)]_n ·(ClO₄)_2n (tacn = 1,4,7-triazacyclononane, 4,4^′-bipy = 4,4^′-bipyridine), has been synthesized and characterized by X-ray crystallography, elemental analysis, IR, electronic spectra, ESR and variable-temperature magnetic susceptibility (4–300 K). The Cu(II) ion is five-coordinated in a distorted square-pyramidal environment to three nitrogens of tacn and two nitrogens from two 4,4^′-bipy ligands. Each 4,4^′-bipy, in which two pyridine rings are slightly twisted, links two [Cu(tacn)]²⁺ units to form 1D zigzag chain. The magnetic behavior shows very weak interaction between metal ions.     

The synthesis and structure of [Sn(NMe2)3Li]∞; an unsolvated polymeric tris(amido)stannate

The reaction of Sn(NMe₂)₂ with LiNMe₂ (1:1 equiv.) gives [Sn(NMe₂)₃Li]_∞ (1). The complex is the simplest tris(amido)stannate to be structurally characterised and the first in which there is no Lewis base solvation of the alkali metal cation; as a result a polymeric structure is obtained in which the stannate anions are involved in bidentate and monodentate coordination of the Li⁺ cations.     

Hydrothermal synthesis, crystal structure and properties of complex [Co (odpa) (phen) 2 ( H2O )] · H2O

以4,4’-氧化二苯四羧酸二酐和1,10-邻菲啰啉为配体在水热条件下合成了标题配合物,并用元素分析、红外光谱、X-射线单晶衍射以及热重分析对配合物进行了表征.晶体结构分析表明配合物为三斜晶系,P-1空间群a=11.190(2)(A),b=12.587(2) (A),c=13.097(3)(A),α=102.688(3)°,β=105.751(2)°,γ =92.615(2)°,V =1721.1(6)A3,Z=2.配合物为单核结构,相邻的单核分子通过氢键的识别作用形成一维超分子双链.π…π堆积作用和C-H…π之间弱相互作用将邻近超分子双链的进一步扩展为三维超分子结构.     

Experimental and DFT calculated structure of the diruthenium(2.5) complex [(Me3TACN)Ru(μ-Cl)3Ru(Me3TACN)](PF6)2

The diruthenium(2.5) complex [(Me₃TACN)Ru(μ-Cl)₃Ru(Me₃TACN)]-(PF₆)₂, Me₃TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, has been crystallized for structural characterization. The results are reproduced by density functional theory (DFT) calculations and confirm the sensitivity of the central Ru(μ-Cl)₃Ru core to contacts between the Cl bridging atoms and the co-ligands. The singly occupied MO is characterized as a σ* MO involving the metal d_z² orbitals and a small halide contribution by DFT calculations and EPR.     

The first complex of the pentameric phosphazane macrocycle [{P(μ-NtBu)}2(μ-NH)]5 with a neutral molecular guest: Synthesis and structure of [{P(μ-NtBu)}2(μ-NH)]5(CH2Cl2)2

The reaction of [{P(μ-N^tBu)}₂(μ-NH)}₅I]⁻[Li(thf)₄]⁺([1 · I]⁻[Li(thf)₄]⁺) with NaOMe in CH₂Cl₂ gives the title compound [{P(μ-N^tBu)}₂(μ-NH)]₅(CH₂Cl₂)₂ [1 · (CH₂Cl₂)₂] the first adduct containing this type of macrocyclic phosph(III)azane host and a neutral guest.     

Synthesis of the dimeric μ2-O aminoalkoxy complexes of rhenium [(CO)3Re(μ2-O∩NH2)]2 and their condensation products with acetone [(CO)3Re(μ2-O∩N=CMe2)]2

The allyl rhenium complex Re(CO)₄(η³-C₃H₅) (1) reacts with the amino alcohols 2-amino ethanol, 1-amino-propane-2-ol, 2-amino phenol and 2-amino benzyl alcohol (2a–d) to give the dimeric μ₂-O-bridged tricyclic aminoalkoxy complexes of rhenium of the type [(CO)₃Re(μ₂-O^∩NH₂)]₂ (3a–d). The acidic NH₂ ligand undergoes a condensation reaction with acetone at r.t. forming the corresponding ketimine complexes [(CO)₃Re(μ₂-O^∩N=CMe₂)]₂ (4a–d). The compounds have been characterized by spectroscopic (IR, NMR, MS), analytical (C, H, N) and X-ray diffraction analyses (4a–d).     

A 2-D polymer constructed through bridging acetate,hydroxo, aqua and bipyridine ligands: crystal structure of {[Cu2(μ-CH3COO)(μ-OH)(μ-H2O)(4,4′-bipy)](2H2O)(SiF6)}n

A novel 2-D coordination polymer constructed by μ₂-acetate-O,O^′, μ₂-hydroxo, μ₂-aqua and 4,4^′-bipyridine (bipy) ligands has been synthesized and structurally characterized. Linear 1-D chain built by bridged μ₂-acetate-O,O^′, μ₂-hydroxo and μ₂-aqua units is composed of Cu₂O₂ motifs and syn-anti bridged acetate ligands. The copper atom with a five-coordination has a distorted square-pyramidal geometry completed by two nitrogen atoms from 4,4^′-bipyridine and three oxygen atoms from acetate, hydroxo and water ligands. The strong stacking effect is observed between 4,4^′-bipyridine ligands.