New 3-D La(III)-Cu(II)-containing coordination polymer with a high potential porosity

A new 3-D coordination polymer containing both 3d and 4f ions has been designed. Its chemical formula is La2[Cu(pba)]3(H2O)8 . 8H2O. It crystallizes in the quadratic system, space group I41/a with a = 42.4947(9) Angstrom, c = 16.3378(3) Angstrom, and Z = 16. Its crystal structure can be described as a 3-D molecular framework exhibiting a complex network of interconnected zigzaglike channels. Once crystallization water molecules are removed, this compound presents a high potential porosity and a low density. The porosity has been evaluated using Connolly's algorithm.     

Assembly of a two-dimensional oxalate-bridged heterometallic Co(II)(3)Cr(III)(2) coordination polymer

Reaction of CoCl(2).4H(2)O with Ag(3)[Cr(ox)(3)] (3 : 2 mol/mol) in methanol gives rise to an oxalate-bridged complex [Co(MeOH)(2)](3)[Cr(ox)(3)](2).6MeOH that consists of a rare cloverleaf-like layered structure (12,3-net). Ferromagnetic coupling is operative between the adjacent metal ions through the oxalate bridges.     

Lanthanide(III)-cobalt(II) heterometallic coordination polymers with radical adsorption properties

Two new coordination polymers {[Ln(2)(PDA)(6)Co(3)(H(2)O)(6)] x xH(2)O}(n) [Ln = Nd, x = 7 (1); Ln = Gd, x = 3.25 (2); H(2)PDA = pyridine-2,6-dicarboxylic acid] have been prepared under hydrothermal conditions with Ln(NO(3))(3) x 6H(2)O, CoO, and H(2)PDA in a molar ratio of 2:3:6. X-ray crystallographic analyses reveal that they crystallize in the hexagonal group P6/mcc and exhibit a nanotubular 3D framework. The adsorption experiment shows that 1 and 2 can adsorb radicals, which is proven by electron paramagnetic resonance spectra with the characteristic bands of the radicals at g = 2.006 and 2.005, respectively.     

Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(I)-Cu(II) coordination polymer including pyrrolidine dithiocarbamate ligand

A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σμ～ 0.4 cm(2) V(-1) s(-1).     

三维氰基桥联Cu(I)配位聚合物的模板合成和晶体结构

将(Et4N)3Mn(CN)6和Cu(en)2(ClO4)2反应得到了三维配位聚合物{[Cu(Ⅱ)(en)2*H2O][Cu(I)2(CN)4]}n(en＝乙二胺),用元素分析、ICP分析、IR光谱对配合物进行了表征.X-射线衍射结果表明晶体属单斜晶系,空间群为Cc(#9),晶胞参数a＝14.759(3),b＝7.734(2),c＝14.247(3)(A),β＝112.65(3)°,V＝1500.9(5)(A)3,Z＝4,Dc＝1.916Mg*m-3,F(000)＝868,最终偏离因子R1＝0.0267,wR2＝0.0633.该配合物结构中Cu(I)离子间通过氰基桥联形成三维峰窝样主体骨架结构,而Cu(Ⅱ)配离子[Cu(en)2*H2O]2+被包合在主体内架通道空腔的中央.该配合物的合成是利用[Cu(CN)2]-为建筑砖块,[Cu(en)2*H2O]2+为模板的自组装反应.     

Bis(oxalato)chromium(III) complexes: Versatile tectons in designing heterometallic coordination compounds

The mononuclear oxalato-containing chromium(III) complexes of general formula [Cr(AA)(C₂O₄)₂]^? (AA = α-diimine type ligand) are able to produce a large variety of heterometallic complexes by acting as ligands towards either fully solvated metal ions or preformed cationic complexes with available coordination sites. This review focuses on the structural diversity of the polynuclear complexes (oligonuclear and coordination polymers) which are generated by the bis(oxalato)chromate(III) species, with a special emphasis to their magnetic properties.     

A novel three-dimensional coordination polymer constructed with mixed-valence dimeric copper(I,II) units

A novel three-dimensional coordination polymer with a mixed-valence localized copper(I,II) dimeric unit, [Cu2(4-pya)3]n (4-pya = 4-pyridinecarboxylate), was hydrothermally synthesized via a simultaneous in-situa redox and hydrolysis reaction of Cu(II) and 4-cyanopyridine and crystallographically characterized to be a twofold interpenetrated three-dimensional coordination network with a cubic [Cu16(4-pya)12] building unit.     

Uranyl sensitization of samarium(III) luminescence in a two-dimensional coordination polymer

Heterometallic carboxyphosphonates UO(2)(2+)/Ln(3+) have been prepared from the hydrothermal reaction of uranyl nitrate, lanthanide nitrate (Ln = Sm, Tb, Er, Yb), and phosphonoacetic acid (H(3)PPA). Compound 1, (UO(2))(2)(PPA)(HPPA)(2)Sm(H(2)O)·2H(2)O (1) adopts a two-dimensional structure in which the UO(2)(2+) metal ions bind exclusively to the phosphonate moiety, whereas the Ln(3+) ions are coordinated by both phosphonate and carboxylate functionalities. Luminescence studies of 1 show very bright visible and near-IR samarium(III)-centered emission upon direct excitation of the uranyl moiety. The Sm(3+) emissive state exhibits a double-exponential decay with lifetimes of 67.2 ± 6.5 and 9.0 ± 1.3 μs as measured at 594 nm, after excitation at both 365 and 420 nm. No emission is observed in the region typical of the uranyl cation, indicating that all energy is either transferred to the Sm(3+) center or lost to nonradiative processes. Herein we report the synthesis, crystal structure, and luminescent behavior of 1, as well as those of the isostructural terbium, erbium, and ytterbium analogues.     

Two- and three-dimensional photoluminescent Cd(II)-carboxylate coordination frameworks bridged by benzenepentacarboxylate and N-donor ligands

Reactions of Cd(OAc)₂·H₂O, benzenepentacarboxylic acid (H₅bpc), 2,2′-bpy/4,4′-bpy, and Et₃N yield two new coordination polymers [Cd₅(bpc)₂(2,2′-bpy)₄(H₂O)₄] (1) and [Cd₅(bpc)₂(4,4′-bpy)₂(H₂O)₄]·3H₂O (2). Complex 1 is a 2-D structure based on six-connected Cd-carboxylate layers. Adjacent layers are linked by π–π interactions and hydrogen bonds to generate a layered supramolecular network. Complex 2 is a 3-D coordination framework. The bpc ligands adopting μ ₇-bridging mode connect Cd(II) ions to form a 3-D open framework with elliptic channels, in which the coordinated 4,4′-bpy ligands fill to support the whole framework. Complex 2 exhibits strong photoluminescence at room temperature.     

Structure and magnetic properties of a new cobalt(II) thiophenedicarboxylate coordination polymer showing unprecedented coordination

A new carboxylato-bridged CoII network of formula {Co((kappa1-kappa1)-(kappa1-mu2)-mu4-TDC)(mu2-H2O)0.5(H2O)}n (H2TDC=2,5-thiophenedicarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and IR and UV-visible spectroscopies. The title compound is made of chains of CoII dimers interconnected by TDC2- ligands, showing an unprecedented asymmetric tetradentate coordination mode of the carboxylate functions. Magnetic measurements show weak ferromagnetic interactions between the Co ions within the dimers.     

Water-induced reversible dissolution/reorganization transformations of Cu(Ⅱ)-K(I) heterometallic coordination polymers

Three new heterometallic coordination compounds, namely, [KCu(I3)(L)2(H2O)2]n(1), [KCu(I3)(L)2(H2O)]n(2) and [CuK4(I3)2(L′)4]n(3), were prepared and characterized(HL=5-methylpyrazine-2-carboxylic acid, HL′=p-tolylacetic acid). Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K4O8]. These chains are further linked each other via rare(1,1,3,3)-triiodide ion-bridging units to generate a 3D(4,5,6)-connected net with the point symbol of {12}2{4·122}4{46}{48·62}4{49·66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu(L)2(H2O)]n·3nH2O. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.     

Crystal structure and spectroscopic study of novel two- and three-dimensional photoluminescent Eu(III)-adipate compounds

Two new photoluminescent compounds with the formulas of [Eu(2)(adipate)(3)(H(2)O)].H(2)O (1) and [Eu(2)(adipate)(3)(4H(2)O)] (2) were synthesized by using Eu(III) chloride and adipic acid under hydrothermal reaction conditions in aqueous solution. Compound 1, a 3-D layered framework, possesses infinite Eu-O-Eu polyhedral chains and self-assembled adipate ligands between Eu-O layers. Compound 2 has dimeric Eu(2)O(16) units interconnected by adipate ligand, resulting in 2-D open frameworks with a cavity among the ligands. Crystal data 1: monoclinic space group C2/c, with a = 14.2486(12) A, b = 8.2733(7) A, c = 39.298(2) A, beta = 99.530(6) degrees, and Z = 8. 2: monoclinic space group P2(1)/c, with a = 11.661(4) A, b = 14.011(3) A, c = 9.013(4) A, beta = 110.87(3) degrees, and Z = 2. The ligand conformations of two Eu(III)-adipate (1 and 2) compounds present anti/anti/anti, gauche/anti/gauche, and intermediate forms. Both compounds 1 and 2 showed strong red luminescence upon excitation, and their luminescence decay involves the multiphonon relaxation mechanism.     

Assembly of a heterometallic polynuclear Sn(IV)-Cu(I) cluster based on Sn(edt)2 (edt = ethane-1,2-dithiolate) as a metalloligand

Reaction of [Cu(PPh3)2(MeCN)2]ClO4 (1) and Sn(edt)2 (edt = ethane-1,2-dithiolate) in dichloromethane afforded a novel compound [Sn3Cu4(S2C2H4)6(mu3-O)(PPh3)4](ClO4)2 x 3 CH2Cl2 (2), which is the first example of the heptanuclear Sn(IV)-Cu(I) oxosulfur complex with a bottle-shaped cluster core. Complex 2 gives a blue-green luminescent emission in the solid state. Crystallographic data for 2: C87H90Cl8Cu4O9P4S12Sn3, trigonal, space group R3, M = 2682.02, a = 18.156(2) A, b = 18.156(2) A, c = 54.495(10) A, gamma = 120 degrees, V = 15558(4) A3, Z = 6 (T = 130.15 K).     

Direct evidence of nanowires formation from a Cu(I) coordination polymer

In this work we present both spectroscopic and morphological evidence showing one-dimensional organization of [CuBr(HIN)]n (HIN=isonicotinic acid) on surfaces.     

Ag(I) coordination polymer with pyrazine sulfonic acid: synthesis,crystal structure,and fluorescence property

A one-dimensional rigid, linear Ag(I) coordination polymer with pyrazine sulfonic acid, [Ag₂L₂?·?H₂O] _n (L?=?pyrazine sulfonic acid) has been synthesized and characterized by elemental analyses, infrared spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structure determination shows Ag(I) centers linked by bridging pyrazine ligands to give a double-chain structure sustained by weak Ag-O and Ag-N interactions. The sulfonate and pyrazine are all involved in hydrogen bonding interaction. The interactions combine with weak π-π stacking to play deciding roles defining the supramolecular structures. A powder X-ray diffraction study implies good phase purity. Solid-state fluorescence quenching and thermal stability are also discussed.     

Valence-induced assembly of Cu(I)-Cu(II) ions into different discrete coordination architectures by a disk-shaped polypyridyl ligand

The valences of metal ions were found to play key roles in controlling the formation and structures of discrete coordination architectures in a copper and disk-shaped hexa-monodentate ligand system. When Cu(I) and Cu(II) ions react with a polydentate ligand HPDQ, a hexanuclear "double-decker" like discrete "LM(3)M(3)L" coordination architecture (CuI)(6)(HPDQ)(2)(CHCl(3))(8) (complex 1), and a "LM(3)L + LM(3)" composite structure complex (Cu(NO(3))(2))(6)(HPDQ)(3) (complex 2) are formed, respectively.     

Syntheses,crystal engineering,and magnetic property of a dicyanamide bridged three-dimensional manganese(II)-nitronyl nitroxide coordination polymer derived from a new radical

Syntheses, structural characterization, crystal engineering, and variable-temperature magnetic study at fixed field strength of a novel dicyanamide bridged three-dimensional manganese(II)-nitronyl nitroxide compound, [Mn(II)(NIT-tz)(dca)(2)] (1), (NIT-tz = 2-(2-thiazole)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxy-3-oxide, a new Ullman type radical) have been described. The compound crystallizes in the orthorhombic P2(1)2(1)2(1) space group with the following unit cell parameters: a = 11.015(2) A, b = 12.6134(14) A, c = 13.7652(9) A, and Z = 4. In this complex, the radical behaves as a bidentate chelating ligand, while four single end-to-end dicyanamide (dca) units construct the three-dimensional structure. Inside the structure, there exist diamond-shaped channels, spiral networks, and helical chains. Variable-temperature (5-300 K, 1 T) magnetic susceptibility data reveal the existence of antiferromagnetic interaction in this molecule. The magnetic behavior is explained by considering the exchange-coupled manganese(II)-radical system, which is subjected to the Mn(II)-dca-Mn(II) intermolecular interactions (H = -2JS(1).S(2) - 2zJ'S). The least-squares fitting of the data results J = -73 cm(-)(1), g = 1.99, and J' = -0.17 cm(-)(1) (z = 4).     

A three-dimensional coordination polymer featuring effective ferrimagnetic hydroxide-bridged manganese(II) chains

A three-dimensional coordination polymer, [Mn3(OH)2Na2(3-cnba)6]n (1) (3-Hcnba = 3-cyanobenzoic acid), has been synthesized by the reaction of MnCl2, NaN3, and 3-Hcnba in water. Its crystal structure was determined by single-crystal X-ray diffraction. Magnetic studies show that the complex behaves as a three-dimensional metamagnet built from effective ferrimagnetic Mn(II) chains in which spin moments are linked by interactions in an AF-F-AF (F = ferromagnetic and AF = antiferromagnetic) sequence in the triangular magnetic repeating unit.     

A coordination polymer of manganese (III) porphyrinate with right-handed helicity and opticity

A first example of 1D coordination polymer [MnTHPP·H₂O·(DMF)₂ (1)] with right-handed helicity and opticity was successfully assembled. Crystal analyses indicate that the right-handed helical assembly is based on coordination bonds from peripheral to center, associating with the saddle distortion of the molecular planes. In its crystal architecture, MnTHPP [manganese (III) ion coordinated by 5,10,15,20-tetra(4-hydroxyphenyl) porphyrin] molecules were ligated each other via the axial coordination between –PhO^? → Mn^III (peripheral to center model, from the peripherally deprotonated hydroxyphenyl to the central metal of the neighbor molecule) to construct the right-handed helices, and the helices are sustained by plentiful hydrogen bonding. Meanwhile DMF molecules are entrapped within the voids among the helices. This is a rare example of the multiporphyrin arrays with right-handed helices bearing opticity.