Syntheses,structures and photocatalytic properties of three copper(II) coordination polymers

Three coordination polymers [Cu₂(obtz)₂(tdc)₂]_n (1), {[Cu(obtz)₂(H₂O)₂][Cu₂(obtz)₂(sip)₂]5.5H₂O}_n (2) and [Cu(obtz)(nip)]_n(3) were synthesized by the hydrothermal reaction (obtz = 1.2-bis(1,2,4-triazol-1-ylmethyl)benzene, tdc = 2.5-thiophenedicarboxylate, sip = 5-sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows a ladder-like one-dimensional chain with two side arms. 2 is comprised of two distinct and crystallographically independent polymeric motifs. The first motif in 2 is the ladder-like one-dimensional anionic chain with two side arms. The second motif in 2 is the cationic chain. 3 exhibits the intriguing 2-fold interpenetrated network based on the undulated 2D (4.4) network. 1, 2 and 3 are good photocatalysts for the degradation of methyl orange (MO) under UV irradiation.     

Two novel Cd(II)-based coordination polymers constructed from isomeric double betaine ligands: Syntheses,structures and fluorescent properties

Two novel Cd^2 + based coordination compounds based on two isomeric double betaine ligands (1,4-Bis(4-carboxylatopyridinium-1-methylene)benzene (H₂L₁Cl₂) and 1,4-Bis(3-carboxylatopyridinium-1-methylene)benzene (H₂L₂Cl₂)) were synthesized, structurally and optically characterized. Both compounds show two dimensional sheet architectures with different features depending on structural motifs that ranging from helical chain to linear chain, and the spatial arrangements of coordinated ligands as well as their unlike coordination modes. They further exhibit the way how three dimensional supramolecular isomers form via weak interactions. Meanwhile, two compounds exhibit intense fluorescence attributing to the ligands' emissions with stokes shift.     

Syntheses,structures and photoluminescence properties of two 2D Cd(II) coordination polymers based on a semirigid tridentate N-donor ligand

The assembly of a semirigid tridentate N-donor ligand with Cd(II) ions afforded two novel coordination polymers, [Cd(tipa)(H₂O)₂·2NO₃·2DMF·H₂O]_n (1), [Cd₂(tipa)₂Cl₄·2DMF·6H₂O]_n (2), where tipa = tris(4-(1H-imidazol-1-yl)phenyl) amine. Structural analyses indicate that the two compounds feature 2D layered networks. A 3-connected uninodal net with point symbol of (8²·10) is constructed in compound 1 by the connection of tipa and metal ions, in which the terminally coordinated water molecules prevent further extension of the layer. Compound 2 features [Cd₂Cl₄] motifs, which are bridged by tridentate tipa ligands into a 2D (3,6)-connected layer. The results show that tipa with different dihedral angles between benzene ring and terminal imidazole groups can act as versatile building blocks for the generation of various networks. Moreover, the photoluminescence properties of 1 and 2 in the solid state at room temperature have been investigated.     

Construction of Zn(II)/Cd(II) coordination polymers derived from a tetrazole derivative: Syntheses,structures and luminescent properties

Three new coordination polymers [Zn(Htip)Cl(H₂O)]_n (1), [Zn(Htip)₂]_n (2) and [Cd(Htip)₂]_n·2nH₂O (3) were synthesized by reactions of Zn(II)/Cd(II) salts with a multidentate tetrazole-based ligand 2-(4-(tetrazol-5-yl)phenyl)imidazo(4,5-f)(1,10)phenanthroline (H₂tip). Complex 1 possesses an infinite 1D coordination chain, and further forms the final 3D supramolecule through π⋯π stacking interactions. Complexes 2 and 3 are isomorphous, and both of them feature an 8-fold interpenetrating 4-connected 3D framework with the dia topological net and the Schläfli symbol of {6⁶}. In 1–3, the Htip⁻ ligand links two metal centers through three terminal N-donors. The structural analyses indicate that the anions and solvents can subtly influence the formation of the resulting network. Moreover, the thermal stabilities and photoluminescent properties of 1–3 are investigated in the solid state.     

Two cobalt(II) coordination polymers based on carboxylate ligand: Preparation,crystal structures and magnetic properties

Two new coordination polymers, [Co₂(L)_1.5(OH)(H₂O)₂]·2H₂O (1) and [CoL(bpp)] (2) (H₂L = 2,5-dibenzoylterephthalic acid and bpp = 1,3-bis(4-pyridyl)propane), have been synthesized and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Their structures were determined by single crystal X-ray diffraction analyses. Complex 1 exhibits a 3D framework assembled from tetra-nuclear cobalt-oxygen bridged by carboxylic O atoms with a (4¹²·6³) topology. Complex 2 possesses a 2D layered structure which extends into a 3D architecture via C–H···π interaction between propane proton and the phenyl ring or pyridine ring of an adjacent sheets. Furthermore, the magnetic properties of them are discussed.     

Syntheses,structures and photocatalytic properties of two coordination polymers based on bis(1,2,4-triazol-4-ylmethyl)benzene and multicarboxylates

Two coordination polymers {[Cu₄(OH)₂(btrb)₂(btc)₂]·4H₂O}_n (1) and {[Cd₂(btrb)(adc)₂(H₂O)]·H₂O}_n (2) were synthesized with hydrothermal method and characterized (btrb = 1,4-bis(1,2,4-triazol-4-ylmethyl)benzene, btc = 1,3,5-benzenetricarboxylate, adc = 1,3-adamantanedicarboxylate). 1 shows an unusual (3,10)-connected two-dimensional metal–organic framework based on the tetranuclear copper(II) cluster [Cu₄(μ₃-OH)₂]. 2 is an interesting three-dimensional network based on the one-dimensional metal–organic nanotube. 1 shows good photocatalytic activity for the degradation of methyl blue (MB). The luminescence of 2 was investigated.     

Two chiral coordination polymers constructed from (1R,2R)-1,2-diaminocyclohexane derivative: Syntheses,structures and properties

Two chiral coordination polymers were synthesized by using a chiral ligand (1R,2R)-1,2-bis(4-(1,2,4-triazolyl))cyclohexane to assemble with Zn(II)/Ag(I) salts. The different coordination modes of the ligand result in two diverse structures, such as a 0D structure for 1 and a 1D chain for 2, respectively. The chiral nature of compounds 1 and 2 was confirmed by circular dichroism spectra (CD) and second harmonic generation (SHG) efficiency measurements. Furthermore, the photoluminescent properties of compounds 1 and 2 have been investigated in the solid state at ambient temperature.     

Syntheses,structures, and luminescent properties of zinc(II) complexes assembled with aromatic polycarboxylate and 1,3-bis(1,2,4-triazol-1-yl)propane

Three new coordination compounds, {[Zn(btrp)(ip)]?2H₂O}_n (1), {[Zn(btrp)(hip)]?2H₂O}_n (2), and {[Zn_1.5(btrp)(btc)(H₂O)]?H₂O}_n (3) (btrp = 1,3-bis(1,2,4-triazol-1-yl)propane, H₂ip = isophthalate, H₂hip = 5-hydroxy isophthalate, H₃btc = benzene-1,3,5-tricarboxylic acid) have been prepared via solvothermal method and characterized by single crystal X-ray diffraction and elemental analysis. 1 possesses 2D (4. 4) net framewok. 2 is also a 2D infinite layer framework, and the resulting 2D structure is interconnected by hydrogen-bond and π…π interactions to lead to a 3D supramolecular architecture. 3 exhibits a novel 2D framework with three nonequivalent points, {5.6²}{5².6}{5⁴.8²}. The fluorescence properties of 1–3 have been studied at room temperature.     

Syntheses,structures and properties of novel d10 coordination polymers based on 4-[(1H-imidazol-4-yl)methylamino]benzoic acid ligand

Complete and partial deprotonation of new ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H₂L) under hydrothermal conditions lead to the formation of two novel coordination polymers [ZnL]_n (1) and [Ag(HL)]_n (2). Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework with (4 · 6²)₂(4² · 6¹⁰ · 8³) topology, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions. Both 1 and 2 show remarkable thermal stability and complex 1 was found to show strong blue luminescence with emission maxima at 381 nm upon excitation at 347 nm in the solid state at room temperature.     

Syntheses, structures, and photoluminescence of two Cd(II) coordination polymers constructed from analogue (pyridyl)imidazole derivative and polycarboxylate acid

Two novel Cd(II) coordination frameworks based on a semirigid asymmetric ligand L and aromatic multi-carboxylate ligands, {[Cd₂L(btc)(H₂O)₂]·5H₂O}_n (1) and [Cd₂L₂(bdc)]_n (2) (L = (4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, H₃btc = 1,3,5-benzenetricarboxylic acid, H₂bdc = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized, and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography. Due to various coordination modes and conformations of the semirigid asymmetric ligand, and carboxylate containing co-ligands, therefore, the two complexes exhibit structural and dimensional diversity. Complex 1 exhibits a novel 2D (3, 5)-connected network structure with (3·5²)(3²·5³·6⁴·7) topology. Complex 2 exhibits a novel 3D CdSO₄ topology, which is formed from different dinuclear cadmium units. In addition, the photoluminescence properties of the free ligand L, and complexes 1 and 2 were studied in the solid state at room temperature.     

Syntheses,crystal structures,and magnetic studies of two cobalt(II) coordination polymers based on concurrent ligand extension

An ether bridged tetracarboxylic acid ligand, 5-(3′,4′-Dicarboxylphenoxy)-isophthalic acid (H₄L) was used to construct two Co(II) coordination polymers in presence of different nitrogen donor ligands such as 4,4′-bipyridine (4,4′-bpy) and 4,4′-bis(pyrid-4-yl)biphenyl (bpbp). The products formed under hydrothermal conditions are formulated as [Co₂L(4,4′-bpy)₂(H₂O)₃]_n (1) and {[Co(bpbp)₂(H₂L)]·H₂O}_n (2). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis, and powder X-ray diffraction (PXRD) measurement. Compound 1 shows an intriguing (3,4,5)-connected 3D framework with a point symbol of (4² · 6² · 8²)(4² · 6⁵ · 8³)(6² · 8). Compound 2 is an unusual 3D supramolecular framework generated by the one-dimensional [Co(bpbp)(H₂L)]_n polymer chain. The magnetic properties of compounds 1 and 2 were examined, indicating antiferromagnetic interactions between the cobalt(II) ions in the temperature range of 2–300 K.     

Two novel 3D self-threading coordination polymers with CdSO4 topology: Syntheses,structures and properties

Two new isostructural metal-organic frameworks, namely [Co(HL)(bpp)] · 0.5H₂O (1) and [Zn(HL)(bpp)] · 3H₂O (2) (H₃L = 5-(2′-carboxy-biphenyl-4-ylmethoxy)-isophthalic acid, bpp = 1,3-bis(4-pyridyl)propane), have been hydrothermally synthesized and further characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra and TG analyses. Compounds 1 and 2 exhibit interesting 3D frameworks of (6⁵.8)-CdSO₄ topology with dangling arm (i.e. the uncoordinated 2′-carboxy-biphenyl-4-ylmethoxy group of HL ligand). The remarkable feature of these two compounds is that each dangling arm threads into two 6-membered rings belonging to the 3D net itself, displaying the self-threading character. The magnetic properties of 1 and photoluminescence of 2 have also been investigated.     

Syntheses,structures and luminescence of zinc and cadmium coordination polymers with bis(1,2,4-triazol-1-yl)butane and benzenedicarboxylate

The self-assembly reactions of the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and rigid ligand 1,4-benzenedicarboxylate (bdc) with Zn(II) or Cd(II) give two novel coordination polymers {[Zn(bdc)(btb)](H₂O)₅}_n (1) and {[Cd₂(bdc)₂(btb)(H₂O)₂](H₂O)₇}_n (2). Coordination polymer 1, a supramolecular isomer of [Zn₂(bdc)₂(btb)₂](H₂O)₂ [X.L. Wang, C. Qin, E.B. Wang, Z.M. Su, Chem. Eur. J. 12 (2006) 2680], is a special 2D (6,3) network, with six Zn(II) atoms at six corners and four bdc and two double btb at six edges. Coordination polymer 2 exhibits a distorted 3D cubic topology that is built from dimer Cd₂ units. The blue luminescent emission maxima at 420 and 439 nm for 1, 440 and 455 nm for 2 were observed in the solid state at room temperature.     

Two novel Co(II)-based coordination polymers with hms and pcu nets: syntheses,structures and properties

Two new Co(II)-based coordination polymers, [Co(HL)(H₂O)₂] (1) and [Co(HL)(bpy)]·H₂O (2) (H₃L = 5-((4-carboxyphenoxy)methyl)benzene-1,3-dioic acid, bpy = 4,4′-bipyridine), have been synthesized under hydrothermal conditions. The two compounds have been characterized by single crystal and powder X-ray diffraction analyses, infrared analyses, elemental analyses and thermogravimetric analyses. Compound 1 shows a 3D 2-fold interpenetrating hms framework, whereas compound 2 reveals a typical 3D pcu net. The UV–vis diffuse reflectance spectra of compounds 1 and 2 have been investigated. Moreover, the magnetic susceptibilities of compounds 1 and 2 have been studied.     

Construction of three Cd(II) coordination polymers based on extended pyridyl-tetrazolyl-bifunctional ligands: Structures and luminescent properties

Reactions of Cd(II) with three new pyridyl-tetrazole-bifunctional ligands, 3-(4-(1H-tetrazol-5-yl)phenyl)pyridine (HL¹), 4-(3-(1H-tetrazol-5-yl)phenyl)pyridine (HL²), and 3-(3-(1H-tetrazol-5-yl)phenyl)pyridine (HL³) resulted in three Cd(II) coordination polymers (CPs), namely, [CdL¹₂]_n (1), [CdL²₂]_n (2), and [CdL³₂(H₂O)]_n (3). Although the geometry of L¹ and L² is quite different, the coordination modes of Cd(II) ion and ligand, as well as the SBUs in compounds 1 and 2 are quite similar, thus give rise to 3D frameworks with same (3,6)-connected ant topology. Compound 3 is a 3D framework composed of 1D helical chains and features as (3,5)-connected tcj topology. The results showed that the topologies are largely dependent on the coordination angle between two coordination groups. The thermal stabilities and luminescent properties of compounds 1–3 have also been studied.     

Two helical one-dimensional copper(II) coordination polymers based on N-(2-hydroxylbenzyl)glycine and N-(2-hydroxylbenzyl)-l-alanine: Syntheses,crystal structures and magnetic studies

Two new helical Cu(II) coordination polymers, [Cu(2,2′-bpy)(Hsgly)]Cl · 2H₂O(H₂sgly = N-(2-hydroxylbenzyl)glycine) (1) and [Cu(2,2′-bpy)(Hsala)](NO₃) · 2H₂O(H₂sala = N-(2-hydroxylbenzyl)-l-alanine) (2) were synthesized. Single crystal X-ray diffraction analysis indicated that both complexes showed helical chains arrangement of Cu(II) centers bridged by carboxyl groups. The magnetic measurements showed complex 1 exhibited ferromagnetic interaction while there was no interaction between the Cu(II) centers in complex 2.     

Syntheses and crystal structures of novel silver(I) coordination polymers based on linear or tetrahedral coordination environments

Two coordination polymers containing Ag(I) atoms, {[Ag(3-pia)](PF₆)}_n (1) and {[Ag(3-pia)₂](PF₆)}_n (2) (3-pia = N-pyridin-3-yl-isonicotinamide), have been synthesized using different solvents, and characterized by single X-ray analyses. In compound 1, Ag(I) atoms are linearly coordinated by two 3-pia ligands, resulting in one-dimensional chains. On the other hand, in compound 2, Ag(I) atoms are tetrahedrally coordinated by four 3-pia ligands, resulting in two-dimensional sheets.     

Two rod-based 3-D lead(II) tetrafluoroterephthalate coordination frameworks with sra topology: Syntheses, structures, and properties

Two three-dimensional (3-D) Pb^II coordination frameworks [Pb(BDC-F₄)(CH₃OH)]_n (1) and [Pb(BDC-F₄)(DMF)(CH₃OH)]_n (2) have been prepared by the reactions of Pb(NO₃)₂ with a rigid dicarboxyl compound tetrafluoroterephthalic acid (H₂BDC-F₄) in different solvents. Single crystal X-ray diffraction reveals that both complexes show the unusual rod-based coordination networks with sra topology, although they crystallize in different space groups (C2/c and ). Their spectroscopic, thermal, and fluorescence properties have also been studied.