Crystal structures and magnetism of infinite alternating chains arranged by paddle-wheel dinuclear copper and mononuclear copper units

The crystal structures and magnetic properties of two novel polyclusters {[Cu(3)(tci)(2)(H(2)O)(2)]·12H(2)O}(n) (1) and {[Cu(3)(tci)(2)(H(2)O)(2)]·6H(2)O}(n) (2) (tci = tris(2-carboxyethyl) isocyanurate) are investigated. The X-ray crystallographic analysis reveals that they contain interesting infinite alternating chains of dinuclear paddle-wheel copper and mononuclear copper units arranged in ABBA magnetism exchange mode. Variable-temperature magnetic susceptibility measurements on the two polyclusters show strong antiferromagnetism couplings between copper ions with exchange interactions J = -181.4 cm(-1), zj' = -0.31 cm(-1) for 1, J = -170 cm(-1), zj' = -0.42 cm(-1) for 2. With the aim of studying magneto-structural correlation, we synthesized a three-dimensional polymer [Cu(3)(tci)(2)(py)(4)(H(2)O)(2)](n) (3) based on isolated dinuclear cluster and mononuclear copper units. Fitting the susceptibility data yielded J = -176.1 cm(-1), zj' = -0.084 cm(-1) for 3.     

New metal–organic architectures of cobalt(II), nickel(II) and zinc(II) with tripodal ligand 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid

Four new coordination polymers {[Ni(HL)(H₂O)]·H₂O}_n (1), {[Co(HL)(H₂O)]·H₂O}_n (2), {[Co(HL)]·4H₂O}_n (3) and {[Zn(HL)]·2H₂O·0.5C₂H₅OH}_n (4) [H₃L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid] have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction analyses. Complexes 1 and 2 display (3, 3)-connected 2D network with (4, 8²) topology. While 3 and 4 exhibit a binodal (3, 6)-connected 2D network with a Schläfli symbol (4³)₂(4⁶, 6⁶, 8³). The complexes 1–4 show remarkable thermal stability and 4 exhibits blue fluorescence with maximum emission at 413 nm upon excitation at 362 nm in the solid state at room temperature. In addition, the magnetic measurements of 3 indicate that there are antiferromagnetic interactions between the neighboring Co(II) centers.     

Distinct structures of coordination polymers incorporating flexible triazole-based ligand: topological diversities, crystal structures and property studies

Six new coordination polymers, namely {[Zn(btec)(0.5)(btmb)]·2H(2)O}(n) (1), {[Co(btec)(0.5)(btmb)(H(2)O)]·3H(2)O}(n) (2), {[Cu(btec)(0.5)(btmb)]·H(2)O}(n) (3), {[Cu(4)(btc)(4)(btmb)(4)]·H(2)O}(n) (4), {[Co(3)(bta)(2)(btmb)(2)]·2H(2)O}(n) (5), [Co(Hbta)(btmb)](n) (6) (H(4)btec = 1,2,4,5-benzenetetracarboxylate, H(3)btc = 1,3,5-benzenetricarboxylate, H(3)bta = 1,2,4-benzenetricarboxylate and btmb = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl), have been successfully synthesized under hydrothermal conditions. All these complexes were structurally determined by single-crystal X-ray diffraction, elemental analysis, IR, TGA and XRD. Crystal structural analysis reveals that 1 is the first example of an unusual 3D framework with (8(6)) topology containing a 2D molecular fabric structure. Complex 2 exhibits a 3D NbO network with (6(4)·8(2)) topology. In 3, Cu(II) ions are coordinated by anti-conformational btmb ligands to form left- and right-handed double helices, which are further bridged by the 4-connected btec(4-) anions to give a 3D porous network. Complex 4 presents a rare 3D gra network structure with (6(3))(6(9)·8) topology. 5 and 6 were obtained through controllable pH values of solution, 5 features a scarce binodal (3,8)-connected tfz-d framework with the trinuclear Co(II) clusters acting as nodes, whereas 6 has an extended 2D 4(4) grid-like layer and the adjacent 2D layers are interconnected by strong hydrogen bonding interactions into a 3D supramolecular framework. The structural diversities indicate that distinct organic acid ligands, the nature of metal ions and the pH value play crucial roles in modulating the formation of the resulting coordination complexes and the connectivity of the ultimate topological nets. Moreover, magnetic susceptibility measurement of 5 indicates the presence of weak ferromagnetic interactions between the Co(II) ions bridged by carboxylate groups.     

Synthesis,structure and dielectric properties of a novel Gd coordination polymer based on 2-（ pyridin-4-yl ）- 1H-i midazole-4,B -dicarboxylate

A new Gd coordination polymer based on 2-（pyridin-4-yl）-I H-imidazole-4,5-dicarboxylate （H3PIDC） has been synthesized under hydrothermal conditions, formulated as {[Gd3（HPIDC）3（PIDC）（H2O）4].3H2O}n （1）. The compound crystallizes in the monoclinic system, space group C2/c with a=20.951（7）, b = 9.515（3）, c = 27.483（10） A,β= 106.176（6）°, Z = 4, V= 5262（3） A3, C40 H45 Gd3 N12 O30, Dc = 2.071 g/cm3, Mr=1645.63, λ （MoKa）=0.71073A, μ=3.846mm-1, F（000）=3204, the final R=0.0390 and wR= 0.1332. Complex 1 is a two-dimensional MOF built up from T-shaped 3-connected HPIDC2 , PIDC3 and 4-connected metal nodes. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.     

Syntheses and characterization of inorganic–organic hybrids with 4-(isonicotinamido)phthalate and some divalent metal centers

Four new inorganic–organic hybrid frameworks [Mn(L)(H₂O)₂]_n (1), {[Co(L)(H₂O)₃]·2H₂O·CH₃OH}_n (2), {[Zn(L)(H₂O)]·H₂O}_n (3) and [Cd(HL)₂]_n (4) [H₂L = 4-(isonicotinamido)phthalic acid] have been synthesized and characterized by single-crystal X-ray diffraction analysis. Complex 1 has three-dimensional (3D) structure and topology related to SrAl₂ (sra) with Schläfli symbol of (4²·6³·8). And 2 displays (3,3)-connected two-dimensional (2D) network with (4,8²) topology, while 3 exhibits a uninodal (3,3)-connected (6,3) 2D network, which is further linked by N–H?O hydrogen bonding interactions to give 3D structure with hms topology and Schläfli symbol of (6³)(6⁹·8). Complex 4 with partial deprotonated HL⁻ ligands also has a 2D network structure. In addition, the magnetic property of 1, nonlinear optical property of 3 and photoluminescence of 3 and 4 were investigated.     

Three novel lanthanide complexes with imidazole-4,5-dicarboxylate ligand: Hydrothermal syntheses, structural characterization, and properties

Three novel lanthanide complexes, namely, [Ce(Himdc)(H₂imdc)(H₂O)₃]·H₂O (1), {[Dy(Himdc)(Ox)_0.5(H₂O)₂]·H₂O}_n (2), and {[Nd(Himdc)(Ox)_0.5(H₂O)₂]·H₂O}_n (3) (H₃imdc = imidazole-4,5-dicarboxylic acid, Ox = oxalate), have been successfully prepared by the assembly of lanthanide ions and H₃imdc ligand under different synthetic conditions. All of the complexes have been characterized by means of elemental analysis, IR, TG analysis, luminescence spectroscopy as well as single-crystal X-ray diffraction analysis. The 3D supramolecular structure of 1 is constructed from 1D zig-zag chains through the hydrogen bonding interactions. Complex 2 possesses the chair-shaped secondary building units (SBUs) with Dy₆(Himdc)₄(Ox)₂ and meso-helical chains (P + M), resulting in a novel 2D structure based on the linkages of oxalate ligand. Complex 3 also presents 2D layer structure with uninodal 6-connected net topology, but crystallizes in the different space group and owns higher coordination number of the central metal atom than complex 2. The luminescence property of 2 is investigated in the solid state at room temperature.     

Novel dinuclear and polynuclear copper(II)-pyrazine-2,3-dicarboxylate supramolecular complexes with 1,3-propanediamine, N,N,N′,N′-tetramethylethylenediamine and 2,2′-bipyridine

Three novel Cu(II)-pyrazine-2,3-dicarboxylate complexes with 1,3-propanediamine (pen), [Cu₂(μ-pzdc)₂(pen)₂] · 2H₂O (1), N,N,N′,N′-tetramethylethylenediamine (tmen), {[Cu(μ-pzdc)(tmen)] · H₂O}_n(2), and 2,2′-bipyridine (bipy), {[Cu(μ-pzdc)(bipy)]·H₂O}_n(3) have been synthesized and characterized by means of elemental and thermal analyses, magnetic susceptibilities, IR and UV/vis spectroscopic studies. The molecular structures of dinuclear (1) and polynuclear (2 and 3) complexes have been determined by the single crystal X-ray diffraction technique. The pyrazine-2,3-dicarboxylate acts as a bridging ligand through oxygen atom of carboxylate group and N atom of pyrazine ring and one oxygen atom of neighboring carboxylate. It links the Cu(II) ions to generate a distorted square pyramidal geometry forming a one-dimensional (1D) chain. Adjacent chains of 1 and 2 are then mutually linked via hydrogen bonding interactions, which are further assembled to form a two and three-dimensional network, respectively. The chains of complex 3 are further constructed to form three-dimensional framework by hydrogen bonding, C–H?π and ring?ring stacking interactions. In the complexes, Cu(II) ions have distorted square pyramidal geometry. Thermal analyses properties and thermal decomposition mechanism of complexes have been investigated by using thermal analyses techniques (TG, DTG and DTA).     

Metal-organic frameworks constructed from 2,4,6-Tris(4-pyridyl)-1,3,5-triazine

Five new metal-organic frameworks based on 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) ligand have been hydrothermally synthesized. Reaction of tpt and AgNO 3 in an acidic solution at 180 degrees C yields {[Ag(Htpt)(NO3)]NO(3).4H2O}n (1).Ag(I) is trigonally coordinated by two pyridyl nitrogen and one nitrato oxygen to form a 1D zigzag chain. Reaction of tpt with CuSO4 affords {[Cu2(tpt)2(SO4)2(H2O)2].4H2O}n (2). Copper(II) is bonded to two pyridyl nitrogen, two sulfato oxygen, and two water oxygen atoms to form an elongated octahedral geometry. Each H2O ligand bridges two copper(II), whereas sulfate bridges copper(II) via micro-1,3 and micro-1,1 fashions. The copper(II)-sulfate-H2O2D layers are linked by bidentate tpt to form a 3D polymeric structure. Reaction of Cu(SO4)2, tpt, and 1,2,4,5-benzenetetracarboxylic acid (H4btec) in the presence of piperidine gives [Cu(tpt)(H2btec)1/2]n (3). Copper(I) is located in a trigonal-pyramidal coordination environment and coordinated by three pyridyl nitrogen of tpt in a plane, whereas a carboxylate oxygen is coordinated to the copper(I) axially. The tpt-Cu forms a layer, and the layers are linked through H 2btec2- to form a 2D double-layered coordination polymer. Replacing CuSO4 with ZnI2 in the synthesis gives {[Zn(tpt)(btec)1/2].H2O}n (4). Zinc(II) is in a distorted tetrahedral geometry and linked through bidentate tpt and exotetradentate btec4- to form a 2D coordination grid. Reaction of tpt with CuCN leads to the assembly of a 3D metal-organic framework [Cu3(CN)3(tpt)]n (5). Copper(I) is trigonally coordinated by one pyridyl nitrogen and two cyanides to form an intriguing honeycomb architecture. Luminescence study shows that 1, 3, 4, and 5 have blue fluorescence, which can be assigned to be ligand-centered emissions. Thermal analysis shows that all of these complexes are quite stable, and especially for 4, the framework is stable up to 430 degrees C.     

Synthesis,crystal structure and thermal analysis of supramolecular architectures of copper(II)(2,2′-biimidazole) complexes using dicarboxylate as a coligand

Two new copper(II) complexes {[Cu(H₂biim)(H₂O)(suc)](H₂O)}_n (1) and {[Cu(H₂biim)₂(H₂O)][Cu(H₂biim)₂(glut)](glutH)(NO₃) · 2.5H₂O}_n (2) (H₂biim, 2,2′-biimidazole; suc, succinate dianion; glut, glutarate dianion) have been synthesized and characterized by single crystal X-ray diffraction study and thermal analysis. Complex 1 comprises of 1D zigzag coordination polymers, elongated along the crystallographic b-axis, connected through H-bonding and face-to-face π–π interactions to form a robust 3D network. Whereas complex 2 is built up of bischelated [Cu(II)(H₂biim)₂]²⁺ units, glutarate and nitrate anions and water molecules, held together through an extensive H-bonded system. The resulting 3D supramolecular architecture defines channels which are filled by lattice water molecules and disordered nitrate anions.     

Syntheses, structures and magnetic properties of three Co(II) coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands

Three new cobalt complexes, {[Co₅(tci)₂(bimb)₃(µ₃-O)₂(H₂O)₂]·3DMF·4H₂O} _n (1), {[Co₃(tci)₂(bib)]·2DMF·2H₂O} _n (2) and {[Co(Htci)(bpea)_0.5]·H₂O} _n (3) (H₃tci = tris(2-carboxyethyl)isocyanurate, bimb = 4,4′-bis(imidazol-1-yl)biphenyl, bib = 1,4-bis(imidazol-1-yl)benzene, bpea = 1,2-bis(4-pyridyl)ethane, DMF = N,N′-dimethylformamide), have been successfully synthesized through the assembly of Co(II) ions, H₃tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRPD). Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D → 3D structure with (6⁵·8) CdSO₄ topology. Complex 2 is built from [Co₃(µ₂-O_carboxyl)₂(CO₂)₄] clusters and linear bib ligands, displaying a two-fold parallel interpenetrated (3,8)-connected (4³)₂(4⁶·6¹⁸·8⁴) topology, while complex 3 is a 3D pillar-layered structure involving an infinite -Co-(µ₂-Ocarboxyl)(CO₂)-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indicates that besides spin-orbit coupling of Co(II) ions, there exist antiferromagnetic exchange interactions in Co₅ and Co₃ clusters of 1 and 2, respectively.     

A series of 2D lanthanide (III) coordination polymers constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate

Reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H₃PyIDC) with a series of Ln(III) ions affords ten coordination polymers, namely, {[Ln(H₂PyIDC)(HPyIDC)(H₂O)₂]·H₂O}_n [Ln=Nd (1), Sm (2), Eu (3) and Gd (4)], {[Ln(HPyIDC)(H₂O)₃]·(H₂PyIDC)·H₂O}_n [Ln=Gd (5), Tb (6), Dy (7), Ho (8) and Er (9)], and {[Y₂(HPyIDC)₂(H₂O)₅]·(bpy)·(NO₃)₂·3H₂O}_n (10) (bpy=4,4′-bipyridine). They exhibit three types of networks: complexes 1-4 are isomorphous coordination networks containing neutral 2D metal-organic layers, while complexes 5-9 are isomorphous, which consist of cationic metal-organic layers and anionic organic layers, and complex 10 is a 2D network built up from 4-connected HPyIDC²⁻ anion and 4-connected Y(III) ions. In addition, thermogravimetric analyses and solid-state luminescent properties of the selected complexes are investigated. They exhibit intense, characteristic emissions in the visible region at room temperature.     

Syntheses, structures and physical properties of transition metal-organic frameworks assembled from trigonal heterofunctional ligands

Six novel metal-organic frameworks (MOFs), {Mn(bpydb)(bpyHdbH)}(n) (1) {[Co(2)(bpydb)(2)](H(2)O)(0.5)}(n) (2), {[Ni(0.5)(bpydbH)(H(2)O)](DMF)(2)}(n) (3), {[Cu(2)(bpydb)(2)](H(2)O)(0.5)}(n) (4), {Zn(bpyHdb)(2)}(n) (5) and {[Cd(0.5)(bpydb)(0.5)(DMF)](H(2)O)}(n) (6), were successfully synthesized by assembling transition metal salts with trigonal heterofunctional ligand 4,4'-(4,4'-bipyridine-2,6-diyl) dibenzoic acid (bpydbH(2)) under hydrothermal and/or solvothermal conditions. Compound 1 features a rare 4-fold interpenetrating (3,5)-connected framework with hms-type topology. Isostructural compounds 2 and 4, constructed by M(2)(COO)(4) secondary building units, exhibit a robust 3D framework with alb topological type in 2-fold interpenetrating mode. Compound 3 consists of 2D (4,4) networks, which are further assembled into the new topological framework with the symbol (5(3)·6(2)·8)(5(3)·6(3))(2) through O-HO interactions. Compound 5 manifests a novel 4-connected interpenetrating framework, constructed by 2D (4,4) layers and interbedded N-HO interactions. Non-interpenetrating honeycomb networks are observed in compound 6, and further packed into a 3D framework featuring 1D channels. The magnetic susceptibility of compound 2 indicates antiferromagnetic interactions between cobalt ions. The photoluminescent properties of 5 and 6 were investigated in the solid state at room temperature.     

Synthesis,structures and NLO properties of five non-centrosymmetric coordination compounds from the copper(II)/dps system (dps = 4,4′-dipyridyl sulfide)

The formation, crystal structure and properties of five copper(II) coordination compounds with the angular ligand, 4,4′-dipyridyl sulfide (dps) are described, {[Cu₃(μ-dps)₄(μ-SO₄)₂(SO₄)(H₂O)₅] · 10H₂O}_∞ (1 · 10H₂O), [Cu(dps)₄(H₂O)₂] · (ClO₄)₂ · H₂O (2 · H₂O), {[Cu(μ-dps)₂(DMF)₂](ClO₄)₂}_∞ (3), {[Cu(μ-dps)₂(H₂O)₂] · (NO₃)₂ · 2H₂O}_∞ (4 · 2H₂O) and {[Cu₃(μ-dps)₆(DMF)₂(H₂O)₄] · (NO₃)₆ · (DMF) · 6H₂O}_∞ (5 · DMF · 6H₂O). The topological architectures of all these coordination compounds are strongly dependent on the counteranions, with the aid of guest solvents, and include a chiral 3D non-interpenetrated structure for 1, an acentric mononuclear structure for 2, acentric 2D undulating networks for 3 and 5, and a chiral 1D double-stranded chain for 4. In particular, all these acentric or chiral coordination architectures are generated from an achiral ligand as a building unit, and their second-order non-linear optical (NLO) properties are also studied in this paper.     

Syntheses,characterization, and luminescent properties of four alkaline earth metal–organic frameworks based on two similar N-containing carboxylates

Four coordination polymers {[Ca(3-pa)₂(H₂O)₂]·3H₂O} (1), {[Sr(3-pa)₂(H₂O)₂]·3H₂O} (2), {[Ca(4-pa)₂(H₂O)₄]} (3) and {[Sr(4-pa)(H₂O)₆]·[4-pa]} (4), (3-pa = pyridine-3-carboxylate, 4-pa = pyridine-4-carboxylate) have been synthesized and structurally characterized. Lots of noncovalent interactions were found in the four compounds, aiding the formation of high-dimensional architectures from the low-dimensional structures. Complex 1 and 2 feature similar 1-D chain structures, which adopt face-to-face orientation to form an interesting 2-D network with pipe-like motif. Chain-like water clusters consisting of infinite tetragonal unit are trapped and stabled in the vacuums of the pipelines. The 2-D sheets are further connected into 3-D architecture by noncovalent interactions. Complex 3 has a discrete mononuclear structure, which is further connected into a 3-D framework by hydrogen bonds and π···π interactions. In complex 4, the zigzag-like chain structure units are parallel to each other and pack in ABAB mode to give rise to a 2-D network, which is stabled by π···π stacking and hydrogen bonds. The counteranions in 4 are hosted between the nets and act as “glue” linking the 2-D networks into a 3-D architecture. In addition, the photoluminescence properties of the compounds have been investigated.     

Synthesis, crystal structures and characterization of four coordination polymers based on 5-amino-2,4,6-triiodoisophthalic acid

One homochiral 1D coordination polymer [Cu(ATIBDC)(2,2′-bipy)]·3H₂O·CH₃OH (1) and three achiral 1D coordination polymers: [Cd(ATIBDC)(2,2′-bipy)(H₂O)]·3H₂O (2), [Cd(ATIBDC)(phen)(H₂O)]·4H₂O (3), and [Mn(ATIBDC)(phen)₂]·5H₂O (4) have been synthesized and characterized (H₂ATIBDC=5-amino-2,4,6-triiodoisophthalic acid, 2,2′-bipy=2,2′-bipyridine, and phen=1,10-phenanthroline). Extended high dimensional network architectures are further constructed with the help of weak secondary interactions, such as hydrogen bonding, aromatic stacking, and halogen bonding (C-I…π and C-I…N/O). Complex 1 crystallizes in the monoclinic system with chiral space group P2(1) and exhibits a right-handed 2₁ helical chain structure. The homochirality of 1 was confirmed by CD spectrum. Interestingly, two new configurations of decameric water cluster are found in 3 and 4. The acyclic tetrameric cluster (H₂O)₃(CH₃OH) in 1 and (H₂O)₄ in 2 array into highly ordered helical infinite chains. Thermal stabilities of all the complexes have been studied. Solid state fluorescent properties of the Cd(II) complexes have been explored.     

Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

NO₂ containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO₂) and 2,5-dinitroterephthalate (bdc-(NO₂)₂), afford porous coordination polymers, {[Zn₂(bdc-NO₂)₂(dabco)]·solvents}_n (2⊃solvents) and {[Zn₂(bdc-(NO₂)₂)₂(dabco)]·solvents}_n (3⊃solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn₂ units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃solvents and 3⊃solvents, a rectangle pore surrounded by eight Zn₂ corners contains two and four NO₂ moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me₂CO. Adsorption measurements reveal that dried 2 and 3 adsorb H₂O molecules to be {[Zn₂(bdc-NO₂)₂(dabco)]·4H₂O}_n (2⊃4H₂O) and {[Zn₂(bdc-(NO₂)₂)₂(dabco)]·6H₂O}_n (3⊃6H₂O), showing the pore hydrophilicity enhancement caused by NO₂ group introduction.     

Dipyridyl bridged coordination polymers of Cu(II): Synthesis,crystal structure and magnetic study

Two coordination polymers, [Cu(bpp)(H₂O)₂(ClO₄)₂]_n (1) and {[Cu(bpds)₂(ClO₄)₂] · 1.5(H₂O)}_n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,4′-bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement. Both the coordination polymers display 1D chains with perchlorate anions acting as pendant ligands. In 1 undulated polymers are built by Cu(H₂O)₂(ClO₄)₂ units connected by single bpp and in complex 2 Cu(ClO₄)₂ fragments are linked by pairs of bpds ligands to form a double-stranded chain. The crystal packing evidences polymers of 1 involved in weak H-bonding interactions leading to a 3D supramolecular network. Magnetic study reveals weak antiferromagnetic interactions in both complexes.     

Syntheses, topological analyses and photoelectric properties of Ag(I)/Cu(I) metal-organic frameworks based on a tetradentate imidazolate ligand

A new tetradentate imidazolate ligand 1,1′,1″,1′′′-(2,2′,4,4′,6,6′-hexamethylbiphenyl-3,3′,5,5′-tetrayl)tetrakis(methylene)(1H-imidazole) (L) and four Ag(I)/Cu(I) coordination polymers, namely [(MCN)₃L]_n (1: M=Ag; 2: M=Cu), and [(MSCN)₂L]_n (3: M=Ag; 4: M=Cu) are described. All four new coordination polymers were fully characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Compound 1 features a 3D supramolecular framework constructed by 1D chains through inter-chain Ag-N(CN) and inter-layer Ag-N(L) weak interactions with an uninodal 6⁶ topology. Complex 2 presents a 3D framework characterized by a tetranodal (3,4)-connected (3·4·5·10²·11)(3·4·5·6·7·9)(3·6·7)(6·10²) topology. Complexes 3 and 4 are isostructural, and both have a 3D network of trinodal 4-connected (4·8⁵)₂(4²·8²·10²)(4²·8⁴)₂ topology. The luminescent properties for these compounds in the solid state as well as the possible ferroelectric behavior of 1 are discussed.     

Synthesis,structure and properties of supramolecular Mn,Co, Ni and Zn complexes containing Salen-type bisoxime ligands

Four supramolecular complexes [MnL¹(H₂O)₂] (1), {[CoL²(OAc)(H₂O)]₂Co}·5CH₃CH₂OH (2), {[NiL³(OAc)(CH₃OH)]₂Ni}·2CH₃COCH₃·2CH₃OH (3) and {[ZnL²(OAc)]₂Zn}·CHCl₃ (4), have been synthesized and characterized by elemental analyses, IR, UV–Vis spectra and X-ray diffraction techniques. All the complexes have the trinuclear configuration except for Mn^II complex being mononuclear configuration. Every trinuclear complex contains two acetate ions coordinate to the three metal ions via a familiar M–O–C–O–M (M = Co, Ni, Zn) coordinated mode. Although complexes 1 and 3 display 1D supramolecular chains, the different coordination environments (mononuclear in 1, trinuclear in 3) provoke divergence in the structures and aggregations of the chain subunits. Complex 2 forms a 3D hydrogen-bonding supramolecular networks possessing a channel composing of six O–H···O hydrogen bonds, while complex 4 exhibits a 2D hydrogen-bonding supramolecular networks with the formation of “grottos” occupied by chloroform molecules through intermolecular hydrogen-bond interactions. The spectral properties of the title complexes have been further discussed in detail.     

Remarkable solvent effects in the hydro‐ and solvothermal synthesis of copper‐1,10‐phenanthroline complexes

Compound {[Cu(II)/Cu(I)]₂(ophen)₄(Htpt)}^?2H₂O ( 1 ) was obtained by hydrothermal reaction. Compound 1 is a mixed‐valence copper coordination complex with a different coordination environment. The X‐ray structural analysis of 1 revealed two crystallographically independent dimeric [Cu₂(ophen)₂]⁺ units bridged by two µ₁‐carboxylate groups of the tpt ligand into a butterfly‐shaped molecule in the crystal structure. Compound [Cu(I)₃(CN)₃(phen)₃] ( 2 ) was synthesized using ethanol instead of water, and consisted of an infinite helix chain formed from [Cu(I)(phen)]⁺ units bridged by cyano groups. Copyright © 2007 John Wiley & Sons, Ltd.