Structure and Photosynthetic Mimicking of Bis（2,6—bis（benzimidazol—2—yl）pyridine）manganese（Ⅱ）

Mn(bzimpy)2(1)[bzimpy=2,6-bis(benzimidazol-2-yl)pyridine],a mononuclear manganese(Ⅱ）complex,was synthesized by the reaction of Mn(OOCMe)2 with bzimpy in absolute ethanol.The complex was structurally characterized by elemental analysis,cyclic voltammetry,and X-ray crystallography.In the complex,the manganese-nitrogen distances were different,and the geometry and the metal ion environment showed the distortion.The cyclic voltammetric measurements have been performed to assess its redox characteristics.The presence of oxidation wave at 0.62V and 0.081V vs.SCE or 0.8V and 1.0v vs.NHE suggested that this complex could catalyze the oxidation of water,therefore,simulate the water-oxidizing complex(WOC) of photosystem Ⅱ (PS Ⅱ).The measurements of photoreduction of 2,6-dichlorophenolindophenol (DCPIP),and oxygen evolution in the manganess-depleted and the comples 1-reconstituted PS Ⅱ preparations just support our conjecture.     

Syntheses and Anti—inflammatory Actiobn of （η—C5H5）2Ti （Cin）2 and （η—C5H5）2Ti（Tzea）2

Two new Complexes(Cp)2Ti(Cin)2and (CP2)Ti(Tzea)2(CP=Cyclopentadienyl η^5-C5H5)have been synthesized in THF by the reaction of HCin(Cincofen,2-phenylquinoline-4-carboxylic acid)or HTzea(5-phenyltetrazolyl-2-ethanoic acid)with(Cp)2TiCl2,and characterized by elemental analyses,IR,1H NMR and 13C NMR,UV spectra,molar conductivity,TGDTA.In the complexes the carboxyl groups are coordinated to Ti(IV)in a monodentate manner,The inhibitory actions of the complexes on mice ear tumefaction caused by croton oil and the rat foot granulation growth produced by cotton wool are higher than those of the corresponding ligands HCin,HTzea and [(Cp)2TiCl2],while their toxicities are lower than those of the free ligands.ηη     

Synthesis and Crystal Structure of aNovelPolythiotungstate Compound[PPh4]2[（S）2W（μ—S）2（O）W（THF）（μ—S）2W（S）2]

1 INTRODUCTION Polythiotungstate complexes can be prepared from the protonation of one sulfur atom of [WS4]2－ and subsequent intramolecular redox reactions[1,2]. For example, [(S)2W(m-S)2W(m-S)2W(S)2]2 was formed by the acidification of a diluted aqueous solution of (NH4)2[WS4] with dilute H2SO4[3]. When a diluted aqueous solution containing [WS4]2 was acidified with 0.1mol/L HCl, [(S)2W(m-S)2(O)- W(H2O)(m-S)2W(S)2]2 was formed[4]. [(S)2W- (m-S)2(S)W(m-S)2W(S)2]2 was form…     

Synthesis and Structure of [Cu2（μ—NO2）（aepy）4]（ClO4）3 （aepy=2—（2—Aminoethyl）pyridine）

1 INTRODUCTION There has been great and considerable interest in the study of copper nitrite complexes because they are relevant to the study of copper-containing enzymes involved in the denitrification process[1]; in particular, copper-nitrite complexes are potentially relevant to the nitrite reductases[2] (the enzyme from Achromobacter Cycloclastes) which convert NO2－ to NO and/or N2O. Many attempts have been made to synthesize a variety of copper-nitrite complexes, in which the n…     

A Practical Synthesis of （S）—（＋）—2—（6′—methoxyl—2—naphthyl） propionic Acid

A simplified procedure for enantioselective synthesis of (S)-( )-2-(6′-methoxyl-2-naphthyl)propionic acid ((S)-( )-naproxen), starting from (6-methoxy-α-naphthyl)-1-propanone,with D-mannitol as auxiliary catalyzed by SmCl3 in one-pot is described. The yield is 87.5%(ee value 99%).     

Synthesis and Crystal Structure of Two One—dimensional Chain Copper Complexes [Cu（TTA）2（4,4‘’—azpy）] and [Cu（TTA）2（3,3‘’—azpy）

Two copper complexes [Cu(TTA)₂(4,4′‐azpy)] (1) and [Cu‐(TTA)₂(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm³, D_c = 3.425 g/cm³, γ = 2.113 mm^?1, F(000) = 694, R₁ = 0.0594, wR₂ = 0.1499. The crystal 2 belongs to monoclinic with space group P2₁/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm³, Z = 2, D_c = 1.646 g/ cm³, μ = 1.015 mm^?1, F(000) = 694, R₁, = 0.0535, wR₂ = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands.     

Synthesis and Structure of [Cu（OH）2（H2O）2（4—C5H4N—COOH）2]

1 INTRODUCTION Supramolecular chemistry and crystal engineering of coordination compounds have attracted considerable interests nowadays owing to the fascinating structural diversity and potential applications as functional materials[1,2]. Generally, architectures of supramolecules are formed through hydrogen bonds, ?- ?stacking interaction or other weak interactions between the molecules. Recently, many supramolecular compounds containing silver(I) and copper(II) species have been re-…     

Cobalt(II) and cadmium(II) square grids supported with 4,4′‐bipyrazole and accommodating 3‐carboxyadamantane‐1‐carboxylate

In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ²N²:N^2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)₂]_n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.     

Crystal Structure of a New Triply‐Bridged Cobalt(III) Dimer with 2, 2′‐Dipyridylamine (dipyam), [Co2(μ‐OH)2(μ‐OAc)(OAc)2(dipyam)2]AcO·EtOH

The structure of [Co₂(μ‐OH)₂(μ‐OAc)(OAc)₂(dipyam)₂]AcO · EtOH ( 1 ) has been determined by single‐crystal X‐ray analysis. The cationic complex may be described as a “di(μ‐hydroxo)(μ‐acetato)dicobalt(III)” core with chelating 2, 2′‐dipyridylamine and monodentate acetate ligands. The coordination polyhedron around each cobalt atom is a distorted octahedral. The dimers are linked in the crystal by N‐H···O_{ionic AcO} and C‐H···O_{monodentate AcO} hydrogen bonds. Spectroscopic data are also presented.     

Infinite Coordination Polymers of One‐ and Two‐dimensional Cobalt Acetates

Two coordination polymers of cobalt acetate, [Co₅(O₂CMe)₁₀] ( 1 ) and [Co(O₂CMe)₂(H₂O)] · H₂O ( 2 ), were solvothermally synthesized and characterized by single‐crystal and powder X‐ray diffraction analyses, IR spectroscopy, and elemental analysis. Compound 1 crystallizes in orthorhombic space group Pbcn in two‐dimensional layers, which consist of 12‐membered cobalt rings. Compound 2 crystallizes in monoclinic space group C2/m and exhibits one‐dimensional chains, which are bridged by one water molecule and two acetate ligands in (2.11)‐ and (2.20)‐modes. Preliminary magnetic studies revealed that antiferromagnetic couplings exist in both compounds.     

A new coordination mode of 6‐methylnicotinic acid in trans‐tetraaquabis(6‐methylpyridine‐3‐carboxylato‐κO)cobalt(II) tetrahydrate

The title compound, [Co(C₇H₆NO₂)₂(H₂O)₄]·4H₂O, contains a Co^II ion lying on a crystallographic inversion centre. The Co^II ion is octahedrally coordinated by two 6‐methylpyridine‐3‐carboxylate ligands in axial positions [Co—O = 2.0621 (9) Å] and by four water molecules in the equatorial plane [Co—O = 2.1169 (9) and 2.1223 (11) Å]. There are also four uncoordinated water molecules. The 6‐methylpyridine‐3‐carboxylate ligands are bound to the Co^II ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O—H...O hydrogen bond, and six strong intermolecular hydrogen bonds of type O—H...O and one of type O—H...N in the packing, resulting in a complex three‐dimensional supramolecular structure.     

Two new CoII coordination polymers with multifunctional 5‐amino‐2,4,6‐tribromoisophthalic acid and flexible isomeric bis(imidazole) ligands: preparation,crystal structure and characterization

Two new Co^II coordination polymers (CPs), namely, catena‐poly[[[(5‐amino‐2,4,6‐tribromobenzene‐1,3‐dicarboxylato‐κO)aquacobalt(II)]‐bis[μ‐1,3‐bis(imidazol‐1‐ylmethyl)benzene‐κ²N:N′]] 4.75‐hydrate], {[Co(C₈H₂Br₃NO₄)(C₁₄H₁₄N₄)₂(H₂O)]·4.75H₂O}_n, (1), and poly[(μ‐5‐amino‐2,4,6‐tribromobenzene‐1,3‐dicarboxylato‐κ²O¹:O³)[μ‐1,2‐bis(imidazol‐1‐ylmethyl)benzene‐κ²N:N′]cobalt(II)], [Co(C₈H₂Br₃NO₄)(C₁₄H₁₄N₄)]_n, (2), have been synthesized successfully by the assembly of multifunctional 5‐amino‐2,4,6‐tribromoisophthalic acid (H₂ATBIP) and Co^II ions in the presence of the flexible isomeric bis(imidazole) ligands 1,3‐bis(imidazol‐1‐ylmethyl)benzene (mbix) and 1,2‐bis(imidazol‐1‐ylmethyl)benzene (obix). The isomeric mbix and obix ligands have a big influence on the structures of CPs (1) and (2). CP (1) is composed of chains of nanometre‐sized elliptical rings, in which the Co^II atom exhibits a distorted octahedral coordination geometry and ATBIP²⁻ acts as a monodentate ligand. Two adjacent chains are interlinked by π–π stacking interactions and hydrogen bonds, resulting in a supramolecular double chain. Hydrogen‐bonded R₈⁶(16) rings extend adjacent supramolecular double chains into a two‐dimensional supramolecular layer. Halogen bonding and a hydrogen‐bonded R₄²(8) ring further link the two‐dimensional supramolecular layers, leading to the formation of a three‐dimensional supramolecular network. The Co^II ion in CP (2) is tetracoordinated, exhibiting a distorted tetrahedral configuration. The ATBIP²⁻ ligand exhibits a bis(monodentate) coordination bridging mode, linking adjacent Co^II ions into zigzag chains, which are further bridged by the auxiliary bridging obix ligand, resulting in a two‐dimensional (4,4) topological network. Interlayer hydrogen and halogen–halogen bonding further extend the two‐dimensional layers into a three‐dimensional supramolecular network. A detailed analysis of the solid‐state UV–Vis–NIR diffuse‐reflectance spectra of (1) and (2) indicates that a wide optical band gap exists in both (1) and (2). CP (1) exhibits an irreversible dehydration–rehydration behaviour.     

Supramolecular architectures in CoII and CuII complexes with thiophene‐2‐carboxylate and 2‐amino‐4,6‐dimethoxypyrimidine ligands

The coordination chemistry of mixed‐ligand complexes continues to be an active area of research since these compounds have a wide range of applications. Many coordination polymers and metal–organic framworks are emerging as novel functional materials. Aminopyrimidine and its derivatives are flexible ligands with versatile binding and coordination modes which have been proven to be useful in the construction of organic–inorganic hybrid materials and coordination polymers. Thiophenecarboxylic acid, its derivatives and their complexes exhibit pharmacological properties. Cobalt(II) and copper(II) complexes of thiophenecarboxylate have many biological applications, for example, as antifungal and antitumor agents. Two new cobalt(II) and copper(II) complexes incorporating thiophene‐2‐carboxylate (2‐TPC) and 2‐amino‐4,6‐dimethoxypyrimidine (OMP) ligands have been synthesized and characterized by X‐ray diffraction studies, namely (2‐amino‐4,6‐dimethoxypyrimidine‐κN)aquachlorido(thiophene‐2‐carboxylato‐κO)cobalt(II) monohydrate, [Co(C₅H₃O₂S)Cl(C₆H₉N₃O₂)(H₂O)]·H₂O, (I), and catena‐poly[copper(II)‐tetrakis(μ‐thiophene‐2‐carboxylato‐κ²O:O′)‐copper(II)‐(μ‐2‐amino‐4,6‐dimethoxypyrimidine‐κ²N¹:N³)], [Cu₂(C₅H₃O₂S)₄(C₆H₉N₃O₂)]_n, (II). In (I), the Co^II ion has a distorted tetrahedral coordination environment involving one O atom from a monodentate 2‐TPC ligand, one N atom from an OMP ligand, one chloride ligand and one O atom of a water molecule. An additional water molecule is present in the asymmetric unit. The amino group of the coordinated OMP molecule and the coordinated carboxylate O atom of the 2‐TPC ligand form an interligand N—H…O hydrogen bond, generating an S(6) ring motif. The pyrimidine molecules also form a base pair [R₂²(8) motif] via a pair of N—H…N hydrogen bonds. These interactions, together with O—H…O and O—H…Cl hydrogen bonds and π–π stacking interactions, generate a three‐dimensional supramolecular architecture. The one‐dimensional coordination polymer (II) contains the classical paddle‐wheel [Cu₂(CH₃COO)₄(H₂O)₂] unit, where each carboxylate group of four 2‐TPC ligands bridges two square‐pyramidally coordinated Cu^II ions and the apically coordinated OMP ligands bridge the dinuclear copper units. Each dinuclear copper unit has a crystallographic inversion centre, whereas the bridging OMP ligand has crystallographic twofold symmetry. The one‐dimensional polymeric chains self‐assemble via N—H…O, π–π and C—H…π interactions, generating a three‐dimensional supramolecular architecture.     

Synthesis,Structure, and Magnetic Properties of a Random Bimetallic One‐dimensional CoII‐MnII Coordination Polymer with Mixed Azide‐carboxylate Bridges

The 3d–3d random bimetallic compound [Co_2.28Mn_0.72(N₃)₆(mpc‐3)₂(CH₃OH)₂] ( 1 ) (mpc‐3 = N‐methylpyridinium‐3‐carboxylate) was synthesized by partly substituting the Co^II ions in the homometallic compound by Mn^II. Complex 1 was structurally and magnetically characterized. It consists of one‐dimensional chains with the neighboring metal ions being linked alternatively by [(μ‐EO‐N₃)₂(μ‐COO)] (EO = end‐on) triple bridges and double EO azide bridges. Hydrogen‐bonding interactions and π–π interactions are involved in the formation of a three‐dimensional supramolecular network. Magnetic measurements revealed that complex 1 exhibits slow relaxation, which is similar to the homometallic Co^II parent compound whereas the T_B is lower than that of the Co^II analog.     

Cobalt(II) and Cobalt(III) Tri‐tert‐butoxysilanethiolates. Synthesis,Properties, Crystal and Molecular Structures of [Co{μ‐SSi(OBut)3}{SSi(OBut)3}(NH3)]2 and [Co{SSi(OBut)3}2(NH3)4][SSi(OBut)3] Complexes

The heteroleptic neutral tri‐tert‐butoxysilanethiolate of cobalt(II) incorporating ammonia as additional ligand ( 1 ) has been prepared by the reaction of a cobalt(II) ammine complex with tri‐tert‐butoxysilanethiol in water. Complex 1 , dissolved in hexane, undergoes oxidation in an ammonia saturated atmosphere to the ionic cobalt(III) compound 2 . Molecular and crystal structures of 1 and 2 have been determined by single crystal X‐ray structural analysis. 1 forms a dimeric molecule [Co{μ‐SSi(OBu^t)₃}{SSi(OBu^t)₃}(NH₃)]₂ with a folded central Co₂S₂ ring and distorted tetrahedral ligand arrangement at both Co^II atoms (CoNS₃ core). The product 2 is composed of the octahedral Co^III complex cation [Co{SSi(OBu^t)₃}₂(NH₃)₄]⁺ and the tri‐tert‐butoxysilanethiolate anion. Within the crystal two pairs of ions interact by hydrogen bonds forming well separated entities. 1 and 2 are the first structurally characterized cobalt thiolates where metal is also bonded to ammonia and 2 is the first cobalt(III) silanethiolate.     

Polymorphism of the dinuclear CoIII–Schiff base complex [Co2(o‐van‐en)3]·4CH3CN (o‐van‐en is a salen‐type ligand)

Reactions of Co(OH)₂ with the Schiff base bis(2‐hydroxy‐3‐methoxybenzylidene)ethylenediamine, denoted H₂(o‐van‐en), under different conditions yielded the previously reported complex aqua[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(II), [Co(C₁₈H₁₈N₂O₄)(H₂O)], 1 , under anaerobic conditions and two polymorphs of [μ‐bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]bis{[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(III)} acetonitrile tetrasolvate, [Co₂(C₁₈H₁₈N₂O₄)₃]·4CH₃CN, i.e. monoclinic 2 and triclinic 3 , in the presence of air. Both novel polymorphs were chemically and spectroscopically characterized. Their crystal structures are built up of centrosymmetric dinuclear [Co₂(o‐van‐en)₃] complex molecules, in which each Co^III atom is coordinated by one tetradentate dianionic o‐van‐en ligand in an uncommon bent fashion. The pseudo‐octahedral coordination of the Co^III atom is completed by one phenolate O and one amidic N atom of the same arm of the bridging o‐van‐en ligand. In addition, the asymmetric units of both polymorphs contain two acetonitrile solvent molecules. The polymorphs differ in the packing orders of the dinuclear [Co₂(o‐van‐en)₃] complex molecules, i.e. alternating ABABAB in 2 and AAA in 3 . In addition, differences in the conformations, the positions of the acetonitrile solvent molecules and the pattern of intermolecular interactions were observed. Hirshfeld surface analysis permits a qualitative inspection of the differences in the intermolecular space in the two polymorphs. A knowledge‐based study employing Full Interaction Maps was used to elucidate possible reasons for the polymorphism.     

Light‐Induced Bidirectional Metal‐to‐Metal Charge Transfer in a Linear Fe2Co Complex

It is a challenge to reversibly switch both magnetism and polarity using light irradiation. Herein we report a linear Fe₂Co complex, whereby interconversion between Fe^III_LS(μ‐CN)Co^II_HS(μ‐NC)Fe^III_LS (LS=low‐spin, HS=high‐spin) and Fe^III_LS(μ‐CN)Co^III_LS(μ‐NC)Fe^II_LS linkages could be achieved upon heating and cooling, or alternating laser irradiation at 808 and 532 nm. The electron spin arrangement and charge distribution were simultaneously tuned accompanying bidirectional metal‐to‐metal charge transfer, providing switchable polarity and magnetism in the complex.