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Five new coordination polymers based on 5,5′-(1,2-phenylenebis(methoxy))diisophthalic acid (H4L), namely [Co3(HL)2(phen)2]n·2nH2O (1), [Mn2L(phen)2]n·2nH2O (2), [Cu2L(4-abpt)2(H2O)2]n·2nDMF (3), [Co2L(bpp)2(H2O)3]n·3nH2O (4) and {(CH3)2NH2[Co2L(μ3-OH)(H2O)2]·DMF·H2O}n (5) (4-abpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, bpp = 1,3-bis(4-pyridyl)propane, phen = 1,10-phenanthroline), have been synthesized and characterized by elemental analyses, IR spectra, PXRD, thermogravimetry and X-ray structural analysis. Complex 1 is a 2D coordination polymer constructing from hexadentate HL3− ligand, which contains trinuclear cobalt cluster [Co3(COO)6] building block. Complex 2 is a 2D coordination polymer assembled by octadentate L4− ligand. Complex 3 is a 3D metal-organic framework assembled by tetradentate L4− ligand and 4-abpt linker. Complex 4 exhibits a 2D layered network containing 1D [Co2L]n nanotube. Complex 5 is a 2D coordination polymer possessing tetranuclear cobalt cluster Co4(μ3-OH)2(COO)4. Tetracarboxylate exhibits five types of coordination modes. Thermal analyses demonstrate that complexes 1 and 2 were thermal stable up to 400–450 °C. Variable-temperature magnetic studies indicate that complex 1 has ferrimagnetic coupling in the [Co3(COO)6] cluster. Complexes 2 and 5 present antiferromagnetic interactions.

The solution reactions of metal salts with (+)-dibenzoyl-tartaric acid (H2L) and 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (4,4′-bipy) afford three two-dimensional (2D) coordination polymers, [Mn2L2(bpp)2(H2O)4]n·nH2O (1), [CuL(bpp)]n·nH2O (2) and [CoL(4,4′-bipy)(CH3OH)(H2O)]n (3). Dibenzoyl-tartrate ligand displays cis- or trans-conformation, and acts as a 1,4-dicarboxylate linker. Complex 1 features a beautiful 2D double-layered (4,4) network containing [Mn4L2(bpp)4] tetrahedral cage. The flexible bpp ligand links Mn(II) to form an interesting 64-membered saddle-shaped macrocycle [Mn4(bpp)4]. Complex 2 displays a 2D wave-like network assembled by 1D [CuL]n linear chain and 1D [Cu(bpp)]n zigzag chain. Complex 3 is a 2D layered network constructing from [CoL(CH3OH)(H2O)]n chain and [Co(4,4′-bipy)]n chain.

Six hydrous Cd(II) coordination polymers based on a scorpion-like 5-(3-pyridylmethoxy)isophthalic acid (H2L), namely {[CdL(H2O)]·2H2O}n (1), [Cd4L4(H2O)4]n (2), [CdL(H2O)]n (3), [CdL(H2O)2]n (4), {[CdL(H2O)]·H2O}n (5) and [CdL]n (6), were hydrothermally synthesized and characterized by EA, IR, PXRD, TG-DSC and X-ray structural analysis. Temperature and solvent play crucial roles in the preparation of the coordination polymers. Complexes 1–3 were prepared in a H2O-DMF (6:2) solvent system at slightly different temperature (85, 100 and 120 °C). Complexes 4–6 were prepared in different H2O-DMF solvents (6:3 and 8:2) and H2O-MeCN (3:6) solvent. These complexes possess different coordinated and/or lattice water molecules, and exhibit structural diversity and various topology nets. Complex 1 is a 2D double-layered coordination polymer. Complex 2 features a 3D porous framework with irl topology. Complex 3 displays a 2D double-layered network. Complex 4 is a 3D coordination polymer with sra topology. Complex 5 exhibits a 3D wave-like framework with sra topology. Complex 6 is a 3D coordination polymer with self-catenated hxg-d topology. 5-(3-Pyridylmethoxy)isophthalate adopts three types of coordination modes. These complexes exhibit higher thermal stability and emit strong luminescence.

Three copper(I) cyanide coordination polymers, namely [Cu8(CN)8(btmb)2]n (1), [Cu(CN)(btmb)0.5]n (2) and [Cu2(CN)2(dpa)]n (3) (btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, dpa = di(4-pyridyl)amine), were synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectra, PXRD and thermogravimetric analyses. Single-crystal X-ray diffraction analyses reveal that complex 1 is an interesting 2D double-layered network constructing from eight distinct Cu(I) centers, eight μ2-cyanides and two tetradentate cis-btmb ligands. Complex 2 is a ladder-like coordination polymer assembled by CuCN linear chain and bidentate trans-btmb linker. Complex 3 has a 2D wave-like network constructing from CuCN zigzag chain and V-shape dpa spacer. These coordination polymers are thermally stable up to 270–300 °C. They emit blue luminescence originating from ligand-centered emission.

Two coordination polymers, [Cu(SCN)(3-ptz)]n (1) and [Cu(SCN)(btmb)]n·nCH3CN (2) (3-ptz = 5-(3-pyridyl)tetrazole, btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene), were synthesized and characterized by EA, IR, PXRD and thermogravimetry. Complex 1 is a 2-D coordination polymer constructed from bidentate 3-ptz and 1,3-thiocyanate ligands. Complex 2 is a 2-D wave-like coordination polymer assembled by bidentate btmb and 1,3-thiocyanate ligands. Acetonitrile guest molecule is perched in the tunnel. Complexes 1 and 2 remain stable up to 240°C and 280°C, respectively. Complex 1 emits strong orange luminescence at 590 nm, and complex 2 emits blue luminescence at 468 nm.

Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu 3 (CN) 3 (tib)] n ( 1 ), [Cu 4 (CN) 4 (tib)] n ( 2 ), and [Cu 2 (CN) 2 (tib)] n ( 3 ), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ 2 -cyanides and a μ 3 -cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 A). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250–350 °C. Complexes 1 – 3 show similar orange emission band at 602 nm originating from LMCT mechanism.

Seven novel coordination polymers based on 2,2′-phosphinico-dibenzoic acid (H3L), namely, {[Zn3L2(H2O)4]·2H2O}n (1), [Zn3L2(4,4′-bipy)2]n (2), [Zn(HL)(2,2′-bipy)(H2O)]n (3), {[Cd9L6(H2O)8]·4H2O}n (4), [Cd8L4(OH)2(OAc)2(4,4′-bipy)]n (5), [Mn3L2(4,4′-bipy)(EtOH)(H2O)2]n (6), and [Mn(HL)(2,2′-bipy)(H2O)]n (7), were synthesized under hydro(solvo)thermal conditions. These compounds crystallize in the triclinic P1 space group for 1, 4, 5, and 6, the monoclinic space group C2/c for 2, and the monoclinic P21/c space group for 3 and 7. The L3– ligand displays versatile binding modes in 1–7. Compound 1 is a one-dimensional (1-D) chain coordination polymer with a three-dimensional (3-D) supramolecular framework. Compound 2 is a 3-D porous metal–organic framework (MOF) with two different 4,4′-bipyridine linkers. Compounds 3 and 7 show 1-D zigzag chain structures. Compound 4 exhibits a sophisticated 3-D MOF constructed from two types of Cd8 clusters and one Cd2 dimer, which is the first example exhibiting the coexist...

Four unique complexes with diverse coordination architectures were synthesized upon complexation of 5,5-(1,4-phenylenebis (methylene))bis (oxy)- diisophthalic acid (H4L) with zinc ions by using different solvent. namely, {[Zn(H2L) (bpp)]·DEF}n (1), {[Zn2(L) (bpp)2]·4H2O}n (2), {[Zn2(L) (pdp)2]·3H2O·DEF}n (3), {[Zn2(L) (pdp)2].4H2O}n (4). Complexes 1,2 and 3,4 are obtained by varying solvents to control their structures. The size of solvent molecular plays an important role to control different structure of these compounds. Compound 1 is 2D waved framework with (4, 4) grid layer as sql topology. Compound 3 displays a (4,6)-connected 2-nodal net with a fsc topology. Compounds 2 and 4 are all three-dimensional network simplified as (4,4)-connected 2-nodal net with a bbf topology. The photochemical properties of compounds 1–4 were tested in the solid state at room temperature, owing to their strong luminescent emissions, complexes 1–4 are good candidates for photoactive materials.

Six coordination polymers based on 5-(3-pyridylmethoxy)isophthalic acid (H2L), namely [Zn2L2]n (1), [Zn2L2(1,3-bix)]n (2), [CdL(1,3-bix)]n·2nH2O (3), [CdL(azpy)0.5(H2O)]n (4), [CdL(btx)0.5]n (5), and [CdL(btmb)]n·2nH2O (6) (1,3-bix = 1,3-bis(imidazol-1-ylmethyl)benzene, azpy = 4,4′-azobispyridine, btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, btmb = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl), have been synthesized and characterized by elemental analyses, IR spectra, PXRD, thermogravimetry and X-ray structural analysis. Complex 1 is a 3D coordination polymer, simplified as a 4-nodal (4,4,5,5)-connected topology net with point symbol {43.63}{43.62.8}{44.65.8}{44.64.82}. Complex 2 is a 3D coordination polymer, simplified as a crs-d topology net with point symbol {6;82}{62;83;10}. Complex 3 is a 2D coordination polymer with a 2-nodal (3,5)-connected topology net. Complex 4 exhibits a 2D double-layered network with a 2-nodal (3,4)-connected topology net, assembled by two parallel [CdL]n layers pillared by azpy spacer. Complex 5 is a 3D coordination polymer, simplified as a 2-nodal (3,8)-connected topology net with point symbol {43}2{46.618.84}. Complex 6 shows a 2D double-layered network with a 2-nodal (3,5)-connected topology net, constructed from wave-like [CdL]n network pillared by btmb spacer. 5-(3-Pyridylmethoxy)isophthalate exhibits five types of coordination modes. Anhydrous or dehydrated substances of 1–6 were thermally stable to 300–400 °C. These Zn(II)/Cd(II) complexes emit blue luminescence originating from ligand-centered emission.

Solvothermal reaction of CuCl 2 ·2H 2 O and 2-(4-pyridyl)benzimidazole (PyHBIm) in a acetonitrile-water mixed solvent afforded a mixture of [Cu I 2 Cu II (CN) 2 (PyHBIm) 2 Cl 2 ] n ( 1 ) and [Cu II (PyH 2 BIm) 2 Cl 4 ] ( 2 ). Complex 1 is a mixed-valence 1D ribbon Cu(I,II)-cyanide coordination polymer. One Cu(II) center linearly links two Cu(I) ions via two μ 2 -CN bridges. XPS spectrum and bond valence sum (BVS) analysis have confirmed the mixed-valence characteristics. Cu(II) ion adopts a centrosymmetric square-planar geometry surrounded by two cyanides and two pyridyl groups. Cu(I) ions adopt a trigonal geometry coordinated by cyanide, imidazole group and Cl − anion. The cyanide ligand is in situ generated from the cleavage of acetonitrile solvent, which indicates that acetonitrile is an environmentally friend cyanating agent. The mechanism of acetonitrile in situ cleavage under solvothermal condition is explained. Complex 2 is a centrosymmetric mononuclear Cu(II) compound. Four equivalent Cl − anions lie on the equatorial plane. The protonated PyH 2 BIm + cation as a monodentate ligand coordinates to Cu(II) center via pyridyl terminal.

A homochiral three-dimensional framework material, [Cu(7)(4-bpt)(6)(CN)(H(2)O)] (1) (4-bpt = 3,5-bis(4-pyridyl)-1,2,4-triazole), has been successfully synthesized by solvothermal reaction, which is generated through an unusual spontaneous asymmetrical crystallization from achiral precursors, and its photocatalytic properties in degradation of organic dyes are also investigated.

In poly[aqua(μ3-benzene-1,4-dicarboxylato-κ5 O 1,O 1′:O 1:O 4,O 4′)[2-(pyridin-3-yl-κN)-1H-benzimidazole]cadmium(II)], [Cd(C8H4O4)(C12H9N3)(H2O)] n , (I), each CdII ion is seven-coordinated by the pyridine N atom from a 2-(pyridin-3-yl)benzimidazole (3-PyBIm) ligand, five O atoms from three benzene-1,4-dicarboxylate (1,4-bdc) ligands and one O atom from a coordinated water molecule. The complex forms an extended two-dimensional carboxylate layer structure, which is further extended into a three-dimensional network by hydrogen-bonding interactions. In catena-poly[[diaquabis[2-(pyridin-3-yl-κN)-1H-benzimidazole]cobalt(II)]-μ2-benzene-1,4-dicarboxylato-κ2 O 1:O 4], [Co(C8H4O4)(C12H9N3)2(H2O)2] n , (II), each CoII ion is six-coordinated by two pyridine N atoms from two 3-PyBIm ligands, two O atoms from two 1,4-bdc ligands and two O atoms from two coordinated water molecules. The complex forms a one-dimensional chain-like coordination polymer and is further assembled by hydrogen-bonding interactions to form a three-dimensional network.

MnII and CoII salts reacting with 4-(4-carboxyphenyl)-4,2′:6′,4″-terpyridine (4-Hcptpy) in DMF/H2O afford two complexes, [Mn(4-cptpy)(DMF)(H2O)2]n·n(4-cptpy)·nDMF (1) and [Co(4-cptpy)2(H2O)2]n (2). Complex 1 is a 1D ribbon coordination polymer assembled by Mn2 dimer and tridentate 4-cptpy ligand. The guest 4-cptpy anion is embedded in 3D supramolecular architecture with strong hydrogen bonds. Complex 2 is a 1D linear chain coordination polymer with quadrangled pores. The complex 1 releases H2O and DMF in 87–150 °C, and the anhydrous [Mn(4-cptpy)]n·n(4-cptpy) remains thermally stable until 403 °C. Variable temperature magnetic susceptibility study in 2–300 K proves that a weak antiferromagnetic interaction exists in the (μ-O2CR)2Mn2 core.

Seven coordination polymers, namely [Mn(4-cptpy)2]n (1), [Co(4-cptpy)2]n (2), [Mn3(4-cptpy)6(H2O)]n·2nH2O (3), [Co(4-cptpy)(HCOO)(H2O)]n·nDMF (4), [Zn2(4-Hcptpy)2Cl4]n·2nC2H5OH·nH2O (5), [Co4(3-cptpy)4(HCOO)4(H2O)2]n (6), and [Mn(3-cptpy)2]n (7) (4-Hcptpy = 4-(4-carboxyphenyl)-4,2':6',4''-terpyridine; 3-Hcptpy = 4-(4-carboxyphenyl)-3,2':6',3''-terpyridine), have been synthesized under hydro(solvo)thermal conditions and structurally characterized. A general solvothermal method is proposed for preparing carboxylate complexes in DMF solution without any basic additive. 1 and 2 possess isostructural 3D metal-organic frameworks containing nanosized cavities. 3 is a beautiful 2D coordination polymer assembled by flower-like Mn3(4-cptpy)6(H2O) subunits. 4 and 6 both display 2D polymeric networks constructed from 4/3-cptpy(-) ligands, in which the formate ligands originate from the hydrolysis of DMF. 5 is a 1D 2(1) helical chain polymer. 7 shows a 2D network with a (3.6) two-nodal kgd topology. 4/3-Hcptpy ligands display seven types of coordination modes. The zinc complex 5 emits strong violet luminescence. 1 and 2 are both thermally stable below 440 °C and exhibit antiferromagnetic interactions.

Six complexes based on a new rigid V-shaped ligand, 2,6-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine (2,6-H2bptp), namely, [Cd4(2,6-bptp)2(d-cam)(l-cam)(H2O)2]n·4nH2O (1), [Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O (2), [Zn(2,6-bptp)(H2O)]n·nH2O (3), [(Mo8O26)Cu2(2,6-H2bptp)2]n (4), [Co(2,6-H2bptp)2][Mo8O26]0.5·5H2O (5), and [(PMo12O40)Ag(2,6-H4bptp)]·2H2O (6) (d/l-H2cam = d/l-camphoric acid; H3btc = 1,3,5-benzenetricarboxylic acid), have been synthesized under hydrothermal conditions. Among these complexes, 2,6-H2bptp adopts seven types of coordination modes; all display a central tridentate chelating plane. Complex 1 possesses a 3D porous metal–organic framework that exhibits an intriguing sandwich-like motif. Complex 2 is a 1D nanorod-like coordination polymer with a square section of 1.11 × 1.06 nm2. Complex 3 exhibits a 1D zigzag chain structure, which is extended to a supramolecular double-chain by hydrogen bonding. In complex 4, polyoxometalate β-Mo8O264– links Cu2(2,6-H2bptp)24+ dimer to form a 1D linear chain...

Hydrothermal reactions of d -(+)-camphoric acid ( d -H 2 cam) and 5,6-dimethylbenzimidazole (dmbi) with metal salts afforded three coordination polymers, namely [Cd 2 ( d -cam) 2 (dmbi) 4 ] n ( 1 ), [Zn 2 ( d -cam) 2 (dmbi)2] n ( 2 ) and [Co( d -cam) 1/2 ( l -cam) 1/2 (dmbi)] n ( 3 ), which were characterized by elemental analysis, IR, PXRD, CD, thermogravimetry and X-ray structural analysis. Complexes 1 and 2 are homochiral coordination polymers. 1 is a 1D left-handed helical chain coordination polymer constructed from tri- and tetra-dentate camphorate. 2 exhibits a 2D polymeric network assembled by tri-dentate camphorate, which belongs to 3-connected {4.8 2 } topology. 3 is a 2D achiral coordination polymer assembled by left- and right-handed 1D Co-camphorate helical chains. It is rarely observed that d -cam ligand changes to l -cam under hydrothermal condition. Three complexes are all thermally stable up to 316–425 °C. 1 and 2 show violet luminescence originating from ligand-centered emission. 3 exhibits an antiferromagnetic interaction in Co II 2 dimer with J = −4.34 cm −1 .

In order to tune the Zn(II) coordination polymer architectures, three position isomers, 1,4- (pbtmb), 1,3- (mbtmb), and 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene (obtmb), and flexible tetracarboxylate ligand, 5,5′-(1,4-phenylenebis(methylene))bis(oxy)diisophthalic acid (H4L1), were used to assemble compounds with different kinds of entangled networks, namely, {[Zn2(L1)(pbtmb)2]·4H2O}n (1), {[Zn2(L1)(mbtmb)2]·4H2O}n (2), and [Zn2(L1)(obtmb)2]n (3). Flexible bis(triazole) ligands present diverse conformations in these compounds. Compound 1 shows a 4-fold interpenetrating three-dimensional architecture with 4-connected mog (moganite) topology. Compound 2 displays a 2D + 2D → 3D polycatenation network simplified as new 4-connected topology with the Schlafli notation of {4,64;8}2{42,64}. Compound 3 is a 2D polythreading structure, in which two layed networks interpenetrate in a (2D/2D) parallel fashion. The powder X-ray diffraction, thermal stabilities, and the photoluminescence of 1–3 have also been investigated.

Reactions of different metal salts with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) gave rise to five new complexes, namely [Cu4(CN)4(3-abpt)2]n (1), [CuBr(3-abpt)]n (2), [CuI(3-abpt)]n (3), [Cu3I3(3-abpt)]n (4) and [Cu(3-abpt)(SO4)(H2O)]n (5). Compounds 1, 3, 4 and 5 are all 2D structures. Compound 1 is a double-layered polymer with an uncommon 3-nodal 3-connected (103)(102.4)4 network, 3 shows a 2D square layered structure, 4 is also a double-layered polymer with 2-nodal 4-connected (3.4.5.62.7)2(3.42.52.7) network and 5 is a 2D structure which is ultimately stacked with an ABAB repeat pattern. Compound 2 is a 1D coordination polymer which exhibits a ladder-like network. The photoluminescence of 1–2 has also been investigated. The long emission lifetimes of 1–2 could be assigned to metal-to-ligand charge transfer triple excited states [MLCT].

On the basis of triangular-shaped [Mn3O] secondary building units, a novel two-dimensional (2D) manganese(III) complex, [NaMnIII3O(sao)3(btec)0.5(H2O)3]·1.25H2O (1) (H2sao = salicylaldoxime, H4btec = benzene-1,2,4,5-tetracarboxylate acid), was synthesized and structurally characterized. The structure of 1 consists of 2D coordination polymer based on [Mn3O] units bridged by sodium ions and benzene-1,2,4,5-tetracarboxylate groups. Magnetic data analysis shows that antiferromagnetic couplings exist between the manganese(III) ions in [Mn3O] subunit of complex 1.

Five novel hybrid compounds, [Mo8O26Cu2(4-abpt)2]n·4nH2O (1), (4-H2abpt)2[Mo8O26] (2), [Mo8O26Cu2(3-abpt)2(H2O)2]n (3), [MoO4Cu(3-abpt)(H2O)]n (4), and [Mo6O19Co(3-abpt)2]n·4nH2O (5) were prepared by reacting MoO3/(NH4)6Mo7O24 with 4-amino-3,5-bis(3/4-pyridyl)-1,2,4-triazole (3/4-abpt) and corresponding metal salts. Compound 1 is a 2D coordination polymer containing extended γ-[Mo8O26]4− and [Cu2(4-abpt)2]4+ ribbons. Compound 2 is a supramolecular hybrid aggregate composed of H-bond linking β-[Mo8O26]4− and 4-H2abpt2+. Compound 3 exhibits a 2D rectangular network constructed by isolated β-[Mo8O26]4−clusters and [Cu2(3-abpt)2]4+. In compound 4, each MoO42− anion links two Cu(II) ions to form a S-type [CuMoO4]n chain, which is further linked by bidentate 3-abpt to form a 2D wave-like network. In complex 5, unprecedented cyclic [Mo6O19]2−cluster links two neighbouring hexamolybdates and two Co(II) ions to form a 2D [CoMo6O19]n network, which is further pillared by tetradentate 3-abpt to generate a 3D metal–organic framework. These compounds are thermally stable under 250 °C. The composites of the final residues were analyzed by PXRD.

Seven new organic–inorganic hybrid compounds containing inorganic polyoxometalates and trigonal organic ligand 2,4,6-tris-(3/4-pyridyl)-1,3,5-triazine (3/4-tpt), namely [Mo8O26M(Htpt)2(H2O)2]n (M = Zn (1), Co (2), Ni (3)), [Mo8O26Cu(Htpt)2(H2O)2]n·2nH2O (4), [Mo8O26(H2tpt)2]·6H2O (5), [Mn(Mo4O13)(4-tpt)2]n (6) and [Fe3(Mo4O15)(3-tpt)]n·nH2O (7), were synthesized hydrothermally and characterized by EA, IR, TG, and PXRD techniques. Single crystal X-ray structural analysis revealed that compounds 1–4 are 1-D coordination polymers constructed from [Mo8O26]4− cluster and [M(Htpt)2(H2O)2]4+ fragments. Compound 5 is an isolated cluster composed of [Mo8O26]4− anion and monodentate H2tpt2+ cation. 3-Tpt ligands in 1–5 are partially protonated and act as monodentate ligands. Octamolybdates adopt β- and γ-[Mo8O26]4− structural mode in compounds 1–4 and 5, respectively. In compound 6, each [Mo4O13]2− tetramer links four Mn(II) ions to form a 2-D wave-like polymeric layer. The 2-D [MnMo4O13] bimetallic layers are pillared by neutral 4-tpt bidentately to generate a 3-D metal–organic framework. Compound 7 is a 3-D coordination polymer constructed from 2-D [Fe3(Mo4O15)] bimetallic polymeric layer and pillared by neutral tridentate 3-tpt. These compounds are thermal stable under 250 °C. The compounds 1 and 5 display luminescence with emission maximum at 481 and 442 nm, respectively.

Three new coordination polymers, [Cu(butca)0.5(bipy)(H2O)] n · 2nH2O (1), [Zn(H2butca) (phen)(H2O)] n · nH2O (2), and [Cd(H2chhca)0.5(phen)(H2O)] n · 2nH2O (3) (H4butca =1,2,3,4-butanetetracarboxylic acid, H6chhca = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid), were prepared and characterized by EA, IR, TG, and X-ray crystallography. Complex 1 is a 1-D double-chain coordination polymer in which tetradentate butca4− coordinates to four Cu(II) ions through four monodentate carboxylates. Complex 2 is a 1-D chain with tridentate H2butca2− coordinating to two Zn(II) ions through monodentate and chelating carboxylates. Complex 3 is a 1-D double-chain coordination polymer. H2chhca4− is octadentate coordinating to four Cd(II) ions through four chelating carboxylates. Hydrogen bonds and π–π stacking interactions play important roles in the formation of supramolecular architectures. The thermal stabilities of 1–3 show dehydrated coordination polymers are thermally stable in the range 260–400°C.

Four novel coordination polymers constructed from flexible pamoic acid, namely [Co(pam)(4,4′-bipy)] n · n H 2 O ( 1 ), [Ni(pam)(4,4′-bipy)(H 2 O) 2 ] n ·2 n CH 3 CN ( 2 ), [Cd(pam)(py) 2 ] n · n py ( 3 ) and [Mn 2 (pam) 2 (py) 6 (H 2 O) 2 ] n ·2 n py ( 4 ), (H 2 pam = pamoic acid, 4,4′-bipy = 4,4′-bipyridine, py = pyridine), have been synthesized and characterized by elemental analysis, infrared spectra and X-ray crystallography. Complex 1 is a 2-D coordination polymer constructed from chelating bis-bidentate pam and 4,4′-bipyridine bridging ligands. Complex 2 is a 2-D coordination polymer assembled by bis-monodentate pam and 4,4′-bipyridine, where acetonitrile is filled in the rectangle channels. Both 2-D coordination polymers display undulated (4,4) grid layers as sql topology. Complex 3 displays a 1-D polymeric chain using chelating bis-bidentate pam as bridging ligand. Complex 4 exhibits an interesting bis-monodentate pam-Mn(II) 1-D polymeric chain, in which exist two-type six-coordinated manganese centers. Mn(1) is bound to four pyridine ligands, whereas Mn(2) is combined to two pyridine and two H 2 O molecules. Their thermal stabilities have been investigated. Cadmium complex 3 displays strong green luminescence with emission maximum at 543 nm.

Two novel three-dimensional (3D) coordination polymers [ Cu 3 II ( mtta ) 6 ] n (1) and [ Cu 2 II Cu 3 I ( trz ) 4 Br 3 ] n ·nH2O (2) (mtta = 5-methyltetrazolate, trz = 1,2,4-triazole) were synthesized and structurally characterized. Complex 1 shows a 3D porous metal–organic framework. By the topology analysis, the complicated architecture of 1 can be simplified to be the 4-connected diamond-type net. Compound 2 is a two-fold interpenetrating 3,5-connected 3D framework with new topology.

Reactions of metal acetates with 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-abpt) and co-ligands gave rise to four new complexes, namely [Zn2(3-abpt)(beta)(DMF) (H2O)2]n·nH2O (1), [Zn(3-abpt)(ip)]n·3nH2O (2), [Zn(3-abpt)(ip)(H2O)2]n·2nH2O (3), and [Cu2(3-abpt)2(C6H5COO)4(H2O)2]n·2nH2O (4) (ip = isophthalate, beta = 1,2,4,5-benzenetetracarboxylate). Compound 1 is a 3D coordination polymer with uncommon 3,4-connected (62.8)2(62.82.102) network. Compounds 2–4 are all 1D coordination polymers, which exhibit diversity structures. Compound 2 is a tubular-like chain, 3 is a ring-like network, and 4 is a zigzag chain. Their thermal stabilities and the photoluminescence of 1 have also been investigated.

Hydrothermal reactions of Cu(II) salts with 2,4,6-tris(3/4-pyridyl)-1,3,5-triazine (3/4-tpt) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) afforded five novel coordination polymers, namely [Cu4(3-tpt)2(btec)2(H2O)4]n·6nH2O (1), [Cu(3-tpt)2(H2btec)]n (2), [Cu3(3-Htpt)2(H2btec)2(btec)]n·4nH2O (3), [Cu2(4-tpt)3(H2btec)2]n·4nH2O (4), and [Cu3(4-tpt)2(Hbtec)2(H2O)]n·3nH2O (5). These complexes exhibit various polymeric networks due to diverse coordination modes of tpt and H4btec. Complex 1 displays a 3-D metal–organic framework in which 3-tpt is an exo-tridentate ligand and μ4-btec4− coordinates to two square-pyramidal Cu(II) and two square Cu(II) ions. Complex 2 is a 1-D chain coordination polymer which contains μ2-H2btec2− bridge and monodentate 3-tpt. Complex 3 shows a 3-D metal–organic framework constructed from protonated bidentate 3-Htpt+, tridentate H2btec2− and tetradentate btec4−. Complex 4 is a 1-D ladder-like coordination polymer assembled by μ2-H2btec2−, mono- and bidentate 4-tpt. Complex 5 exhibits a porous 3-D metal–organic framework constructing from tridentate 4-tpt and μ3-Hbtec3−. Their thermal stabilities were also investigated.

Three new copper(II) azide coordination polymers with derivatives of 1,2,4-triazole as bridging coligands, namely [Cu2(admtrz)2(N3)4]n (1) (admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole), [Cu(4-abpt)(N3)2]n·2nH2O (2) (4-abpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole) and [Cu3(2-ptrz)2(N3)6]n (3) (2-ptrz = 4-(2-pyridyl)-1,2,4-triazole), were prepared and characterized by elemental analyses, IR spectra and X-ray structural analyses. Compound 1 has a 1D chain structure in which Cu(II) ions are bridged by end-on (EO) azides and admtrz ligands. This compound contains three kinds of coordination modes for Cu(II) ions, including tetrahedral, square pyramidal and octahedral geometries. Compound 2 displays an interesting 3D framework structure, in which the azide ligands link Cu(II) ions in end-to-end (EE) mode affording a 2D square layer. This 2D layers are further bridged by bent 4-abpt ligands to form an interesting 3D framework. Furthermore, this structure also exhibits an alpha-Po net topology. Compound 3 displays a 1D rectangle-like chain structure linked by azides adopting end-on (EO) and end-to-end (EE) modes and 2-ptrz ligands. The IR and thermal stabilities of these coordination polymers 1–3 have also been studied.

Three coordination polymers, [Cd3(BTC)2(m-bix)3]n·4nH2O (1), {[Cd(HBTC)(H2O)]·(p-bix)1/2(H2O)2}n (2) and [Zn3(BTC)2(p-bix)3(H2O)2]n·4nH2O (3) (H3BTC = 1,3,5-benzenetricarboxylic acid, bix = bis(imidazol-1-ylmethyl)-benzene), have been synthesized under hydrothermal conditions and structurally characterized. In 1, three Cd(II) ions are all in a highly distorted octahedral coordination environment, and m-bix plays a bidentate bridging ligand. In 2, Cd(II) ion is also in a highly distorted octahedral geometry, but p-bix is not coordinated with Cd(II) ions. p-Bix acts as a guest molecule filling in the Cd-HBTC rectangular channel. The structure of 3 contains two kinds of unique Zn(II) ions, one is in tetrahedral geometry and the other is in ideal octahedral environment. All the three compounds are three-dimensional metal-organic frameworks. Their TG, IR and fluorescent spectra are also reported. Additionally, a new parameter σ is proposed to quantify the distortion of an octahedral environment.

Two new three-dimensional (3D) coordination polymer [Cu2(tetrazolate)3(OH)]n (1) and [Cd2(tetrazolate)3Br]n (2) were synthesized and structurally characterized. By the topology analysis, the complicated architecture of 1 and 2 are all simplified to be the 6-connected pcu-type net. The variable-temperature magnetic susceptibilities (5–300 K) of 1 shows antiferromagnetic interactions of copper(II) ions bridged tetrazolate ligands and/or hydroxide anion.

Hydrothermal reaction of CuCN with 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) affords a wave-like infinite chain coordination polymer [Cu2(CN)2(3-bpo)]n (1). Replacement of 3-bpo by its isomer 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) could yields polymer [Cu(CN)(4-bpo)]n (2). In the complex 1, the bent 3-bpo ligand adopts bidentate chelating mode binds with the Cu(I)-cyanide chain to form 16-membered macrocyclic structure. The complex 2 exhibits a layered metal–organic framework, in which exo-bidentate 4-bpo ligand connects the Cu(I)-cyanide chains to form 2-D rectangle grid. Both of these Cu(I) complexes are thermal stable under 200 °C and release 3-bpo or 4-bpo ligand in 200–360 °C. Luminescent study reveals that 1 has green-light emission, while 2 has blue-light emission.

Hydrothermal reactions of CuCN, K3[Fe(CN)6] with 2,2′-bipyridine, 1,10-phenanthroline or 2,6-bis(1,2,4-triazolyl)pyridine (btp) afford three coordination polymers, [Cu7(CN)7(bipy)2] n (1), [Cu2(CN)2(phen)] n (2) and [Cu3(CN)3(btp)] n (3). Complex 1 displays 1D polymeric ribbons which are assembled through Cu ··· Cu and π–π stacking interactions into a 3D framework. Complex 2 shows a 1D zigzag chain structure in which phen is a side ligand. In 3, the copper cyanide 2D polymeric networks are connected by tridentate btp to form a 3D metal-organic framework. These coordination polymers exhibit strong fluorescent emissions in the solid state.

Hydrothermal reactions of Cu(NO3)2 with 2,6-bis(1,2,4-triazolyl)pyridine (btp) and 1,3,5-benzenetricarboxylic acid (H3btc) or 1,2,4,5-benzenetetracarboxylic acid (H4btec) in base aqueous solution afford two novel complexes [Cu2(btp)(btc)(H2O)(OH)]n (1) and [Cu2(btp)(Hbtec)]n · nH2O (2). Complex 1 is a coordination polymer where a carboxylate and a hydroxyl are bound to Cu(II) ions to form (μ-OH)(μ-O2CR)Cu2 core, which is ferromagnetic couple with 2 J = 21.30 cm−1. Complex 2 is a 3-D coordination polymer. Bond valence sum (BVS) analysis indicates it is a mixed-valence compound. Cu(I) is three-coordinated by triazole N-donors, while Cu(II) is four-coordinated by a triazole N and three carboxyl O-donors. Both complexes are quite thermal stable.

Three polycarboxylate coordination polymers containing 2-(2-pyridyl)benzimidazole as co-ligand, [Cu(Bdc)(2-PyBIm)] n (1), [Cu(HBtc)(2-PyBIm)] n (2) and [Cd2(HBtc)2(2-PyBIm)2] n ·; nH2O (3) (H2Bdc = 1,4-benzenedicarboxylic acid; H3Btc = 1,3,5-benzenetricarboxylic acid), have been synthesized and characterized by elemental analyses, IR spectra, TG-DSC and X-ray structural analyses. Complex 1 is a one-dimensional zigzag chain in which the Cu(II) is cis six-coordinated by two chelating carboxyl groups and a 2-PyBIm ligand. Complex 2 is a two-dimensional (4, 4) network in which H3Btc is partially deprotonated. Complex 3 has a three-dimensional framework in which one Cd(II) is six-coordinate and the other is seven-coordinate. All 2-PyBIm groups are neutral, chelating, bidentate ligands in 1–3. These complexes are quite thermally stable. The luminescence of 3 has also been investigated.

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.

Three supramolecular compounds, [Mn2(chda)(phen)4(H2O)]·(ClO4)2·phen·4H2O (1), [Cu(mal)(bipy)]n·2nH2O (2) and [Cu(ca)2(bipy)]·2H2O (3) (chda = 1,1-cyclohexanediacetate, mal = maleate, Hca = cyanuric acid, bipy = 2,2′-bipyridine), have been synthesized and characterized by elemental analyses, IR spectra, thermal analyses and X-ray structural analyses. Compound 1 is a carboxylate-bridging binuclear complex incorporating uncoordinated 1,10-phenanthroline bonded by hydrogen bonding and π–π stacking interactions. Compound 2 is a 1D zigzag chain carboxylate coordination polymer incorporating cyclic (H2O)4 tetramers of lattice water, which further connect the zigzag chains through strong hydrogen bonds to form 2D supramolecular network. Compound 3 is a mononuclear complex in which H-bonding (H2O)8 water clusters further combine the complex through hydrogen bonds to form supramolecular framework. Thermal stabilities of 1 and 3 have also been investigated.

Hydrothermal reaction of CuCN, K 3 [Fe(CN) 6 ] with 4-(6-amino-2-pyridyl)-1,2,4-triazole (apt) afforded a coordination polymer [Cu 7 (CN) 7 (apt) 2 ] n ( 1 ), while solvothermal reaction of CuSCN with apt in acetonitrile afforded a coordination polymer [Cu 2 (SCN) 2 (apt)] n ( 2 ). Complex 1 shows two-dimensional polymeric network with large hexagonal channels constructing by CuCN chains and tridentate apt ligands. Complex 2 shows two-dimensional polymeric framework assembled by ladder-like [Cu(SCN)] n chains and bidentate apt ligands, in which thiocyanate acts as a tridentate bridging ligand. Both polymers are thermal stable and strong fluorescent in the solid state.

Four copper(I) cyanide coordination polymers containing 2-(n-pyridyl)benzimidazole ligands, namely [Cu2(CN)(2-PyBIm)]n (1), [Cu2(CN)2(3-PyHBIm)]n (2), {[Cu3(CN)3(4-PyHBIm)4] · 2H2O}n (3) and [Cu5(CN)3(4-PyBIm)2]n (4), have been synthesized and characterized by X-ray crystallography. Complex 1 is a one-dimension coordination polymer in which 2-(2-pyridyl)benzimidazole is deprotonated and adopts a bridging tridentate coordination mode. Complex 2 has ladder-like structure in which 2-(3-pyridyl)benzimidazole does not deprotonate and acts as a bidentate bridge. Complex 3 displays a saddle-shaped helical chain constructed through μ2-cyanide group and the outstretched neutral 2-(4-pyridyl)benzimidazole monodentate ligand. Complex 4 shows two-dimension layer polymeric structure in which deprotonated 2-(4-pyridyl)benzimidazole acts as a tridentate bridging ligand. The cyanide groups in four complexes all act as bidentate bridging ligands. These complexes are thermal stable and display luminescence in the solid states.

Two azido-bridged coordination polymers, [Ni(L)(μ1,1-N3)2] (1) and [Cu(L)(μ1,1,3-N3)(N3)] (2) (L = 1,2-diaminocyclohexane), have been synthesized and characterized by elemental analyses, IR spectra and X-ray structural analyses. Complex 1 is a one-dimensional helical chain coordination polymer with both azides as μ1,1-bridge, which exhibits interesting wheel motif. Complex 2 shows two-dimensional layer network in which an azide acts as μ1,1,3-bridge and the other azide as monodentate ligand. Cyclic voltammogram gives quasi-reversible redox wave of Cu(II)/Cu(I) pair. Variable-temperature magnetic property of 1 was investigated, which shown strong ferromagnetic interaction arising from the μ1,1-azido bridging nickel(II) chains.

Two new azide complexes, [Cd2(3-abpt)(N3)4]n (1) and [Cu(3-abpt)2(N3)2] (2) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), have been prepared and structurally characterized. Complex 1 displays an interesting 2D polymeric structure with rarely reported 3,7-connected (32;4)(34;46;56;65) network in the Schafli notation. Complex 2 contains mononuclear pieces, and they are linked each other through weak Cu⋯N coordination bonds to form a 2D sheet with (4, 4) topology. The thermal stability and fluorescent property of 1 have also been investigated.

Hydrothermal reaction of CuCN, K3[Fe(CN)6] and 1,10-phenanthroline affords a novel cyanide-bridged copper(I) coordination polymer [Cu3(CN)3(phen)]n (1). The complex displays an interesting one-dimensional neutral double helical framework with (phen)Cu–CN– side-arms as interchain bridges. The double helical chains are close packed in a parallel fashion, and the phen ligands stack in an interpenetrating mode, which leads to π–π interactions between parallel phen planes. The thermal stability and fluorescent property have also been investigated.

A 2D tri-layer compound {[Co(8)(tbip)(6)(H(2)O)(9)(OH)(4)]·12(H(2)O)}(n) (1) (H(2)tbip = 5-tert-butyl isophthalic acid) consisting of novel heptacobaltate clusters and single cobalt centers bridged by tbip(2-) ligands has been hydrothermally synthesized. The complex represents a rare example of a homometallic coordination polymer built up from both heptanuclear metal clusters and single metal centers simultaneously. The magnetic investigation reveals that the complex exhibits the overall predominance of antiferromagnetic coupling between magnetic centers.

Three inorganic-organic compounds based on [Mo(x)O(y)](n-) chains, [Ag(4)(3-pttz)(2)Mo(3)O(10)] (1) (3-pttz = 5-(3-pyridyl) tetrazolate), [Ag(4)(2-pttz)(2)Mo(4)O(13)] (2) (2-pttz = 5-(2-pyridyl) tetrazolate), and [Ag(4)(pzttz)(2)Mo(4)O(13)] (3) (pzttz = 5-(pyrazinyl) tetrazolate), have been self-assembled, accompanied by in situ formation processes of the 5-substituted tetrazolate ligands under hydrothermal condition. Compound 1 features a 3D framework composed of [Mo(3)O(10)](2-) chains cross-linked by [Ag(4)(3-pttz)(2)](2+) belts. Compounds 2 and 3 reveal the 3D structures based on [Mo(4)O(13)](2-) chains pillared by silver tetrazolate polymeric chains. The three title compounds represent the first three examples that the tetrazolate ligands are introduced into the backbones of the [Mo(x)O(y)](n-) anion chains.