Structures and photoluminescence of coordination polymers assembled from bifunctional ligand containing both tetrazole and imidazole groups

Three new coordination polymers, namely, {[Cu₂(IPT)(SO₄)(OH)(H₂O)]·H₂O}_n (HIPT = 5-(4-(1H-imidazol-1-yl)phenyl)- 1H-tetrazolate, 1), {[Cd₂(IPT)(NPA)(OH)]·H₂O}_n (H₂NPA = 5-nitroisophthalic acid, 2), and {[Zn₂(IPT)(IDC)(H₂O)]·3H₂O}_n (H₃IDC = 1H-imidazole-4,5-dicarboxylic acid, 3), were assembled from a bifunctional organic ligand containing both tetrazole and imidazole groups with/without the aid of carboxylate coligands. Compound 1 possesses 2D structure built by 1D [Cu₂(IPT)(SO₄)(OH)]_n secondary building blocks and IPT⁻ linkers. The 2D networks are linked into 3D supramolecular framework via water chains in helical conformation. Compound 2 displays 3D pillar-layer framework with 2D layers based on tetranuclear Cd(II) SBUs and NPA^2 − pillars. Compound 3 exhibits a 3D framework constructed from the interconnection of 1D [Zn-IDC]_n chains and binuclear Zn₂(IPT)₂ rings. The thermal stabilities of porous compound 3 and luminescent properties of compounds 2 and 3 have also been studied in detail. They exhibit intense solid-state fluorescent emissions at room temperature.     

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.     

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.     

Three-dimensional 3d–4f heterometallic coordination polymer containing Sm2Mn4 clusters: Synthesis,crystal structure and properties

Heterometallic coordination polymers of the form {[SmMn₂(imdc)₂(OAc)(H₂O)]·2H₂O}_n (1) (H₃imdc = 4,5-imidazoledicarboxylic acid, HOAc = acetic acid) were hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The results reveal that 1 has a three-dimensional framework containing Sm₂Mn₄ clusters. The luminescence and magnetic properties of 1 were also investigated.     

A 2D brickwall architecture from a double-T-shaped ligand and hybrid coordinatively unsaturated copper: Synthesis,structure, and framework dynamic

A double-T-shaped ligand (H₄BPTC) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, [Cu₂(BPTC)(Im)₄(H₂O)(DMF)]_n (1) (DMF = N,N-dimethylformamide, H₄BPTC = Biphenyl-3,3′,4,4′-tetracarboxylic acid, Im = imidazole), which exhibits an interesting framework dynamic upon de-/resolvation.     

A new 3D Cd(II) metal–organic framework with discrete (H2O)6 clusters based on flexible cyclohexane-1,2,4,5-tetracarboxylic acid ligand

A 3D metal–organic framework (MOF), {[Cd₂(CTA)(bpp)₂(H₂O)₂] (H₂O)₃}_n (1) (H₄CTA = cyclohexane-1,2,4,5-tetracarboxylic acid, bpp = 1,3-bis(4-pyridyl)propane), has been synthesized and structurally characterized by elemental analysis, IR and powder X-ray diffraction. Single-crystal X-ray measurement reveals that the complex presents three-dimensional frameworks with 1D channels which are filled by unique (H₂O)₆ clusters. Noteworthily, the H₄CTA ligands keep exclusive conformation, where the carboxyl groups adopt different coordination modes, and the bpp ligands perform two different conformations. Thermogravimetric analysis demonstrates that 1 features favorable thermal stability. Photoluminescence property of 1 is investigated in the solid state at room temperature as well.     

Two new isomeric complexes containing a well-resolved 1D water morph and (6, 3)-connected framework through hydrogen bonding interactions

Two new isomeric complexes, namely {[Cu(fum)(tpy)] · 5H₂O}_n (1) and [Cu₂(fum)₂(tpy)₂] · 4H₂O (2), have been synthesized simultaneously from the reaction of Cu(fum) with tpy (where fum = fumarate, tpy = 2,2′:6′,2″-terpyridine) under mild condition. The crystal structures of complexes were determined by X-ray single-crystal diffraction. Complex 1 stabilizes in an unusual 1D water tape notated T4(2)10(2), which is directed by two chiral helical water chains; binuclear complex 2 represents a complicated (6, 3)-connected framework via supramolecular interactions. Additionally, complex 1 exhibits weak ferromagnetic behavior.     

Coordination polymers from 1-D to 3-D assembled from disulfonate ligands: Structures and luminescent properties

Four rare earth organodisulfonate coordination polymers, {[Tb₂(phen)₄(nds)₃(H₂O)₂]·4H₂O}_n (1), {[Ln(phen)(nds)(OH)]}_n[Ln = Sm (2), Nd (3)], {[Tb(phen)₂(nds)_0.5(OH)·H₂O]·(nds)_0.5}_n (4), were synthesized under the solvothermal conditions by using ligands 2,6-naphthalenedisulfonate (L = nds) and 1,10-phenanthroline (L′ = phen). Single-crystal X-ray diffraction reveals that compounds 1 and 4 exhibit different 1-D and 2-D crystal structures just owing to the single difference of stoichiometric ratio of the reactants in the synthesis process. Compounds 2 and 3 show 3-D structures with similar Ln coordination mode. Besides, the photoluminescent property in solid state of 1 was investigated in detail.     

Syntheses and characterizations of two-dimensional polymers based on tetraimidazole tetraphenylethylene ligand with aggregation-induced emission property

Two new coordination polymers [Co(TIPE)(H₂O)₂]·Hbtc·CH₃CN·3H₂O (1) and [Cd(TIPE)_0.5(m-bdc)(H₂O)]·CH₃OH·H₂O (2) (TIPE = tetra(3-imidazoylphenyl)ethylene, H₃btc = 1,3,5-benzenetricarboxylate, m-H₂bdc = 1,3-benzenedicarboxylate) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and PXRD. Furthermore, the luminescent properties of complexes 1, 2 and TIPE ligand have also been investigated in the solid at room temperature.     

Synthesis,structure and magnetic properties of a copper molybdate hybrid inorganic/organic solid with a novel 10-connected three-dimensional network topology

Hydrothermal reaction of CuCl₂, MoO₃, and 4,4′-dipyridylketone (4,4′-dpk) afforded green crystals of the mixed metal oxide phase {[Cu₂(MoO₄)₂(4,4′-dpk)(H₂O)]·H₂O}_n (1). According to single-crystal X-ray diffraction, {Cu₂O₂} dimers link into 1-D {Cu₂O₂(μ-H₂O)}_n chains via bridging aqua ligands. These chains form [Cu₂(MoO₄)₂(H₂O)]_n slabs via linkage through tetrahedral molybdate anions. In turn, the copper molybdate slabs are pillared through tethering 4,4′-dpk ligands into a 10-connected three-dimensional lattice with an unprecedented 3¹²4³⁰5²6 topology. Variable temperature magnetic data above 140 K were fit to the Curie–Weiss law, with C = 0.17 cm³ K/mol Cu and Θ = 70 K, indicating likely ferromagnetic coupling within the dinuclear kernels of 1; low temperature data points towards the possibility of interdimer antiferromagnetic interactions.     

Two novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu2Ln2(ox)(SiW11)2} dimers and [Cu(en)(ox)]/[Cu(en)2] linkers

Two novel 2-D organic–inorganic hybrid silicotungstates [H₂en][Cu(en)₂(H₂O)]₂{[Cu(en)₂]₃[Cu(en)(ox)]₂[Ln₂(ox)(α-SiW₁₁O₃₉)₂]}·nH₂O (Ln = Er^III, n = 10 for 1, Ln = Sm^III, n = 8 for 2) with mixed organic ligands of ox and en (ox = oxalate, en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), power X-ray diffraction (PXRD) and X-ray single-crystal diffraction, respectively. Notably, 1 and 2 are isomorphic and exhibit the first novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu₂Ln₂(ox)(SiW₁₁)₂} dimers and [Cu(en)(ox)]/[Cu(en)₂] linkers. Furthermore, the TG curve of 1 and 2 display three steps of weight loss in the range of 25–1000 °C.     

Novel heterobimetallic Cu/Mn coordination polymers prepared by “direct permanganate” synthesis

Two heterometallic Cu/Mn complexes [Cu(Me₂en)₂][Mn₂(ox)₃] · 2H₂O (1) (Me₂en = N,N-dimethylethylenediamine, H₂ox – oxalic acid) and [Cu(1,3-pn)(ox)(H₂O)][Mn(ox)(H₂O)₂] · H₂O (2) (1,3-pn = 1,3-diaminopropane) are prepared by the one-pot reaction of copper powder, tetrabutylammonium permanganate, oxalic acid and N-chelating ligands. Their structures are investigated by single-crystal X-ray analysis that reveals interesting variation in bridging motives of the oxalate groups composing the Mn-polymeric fragments.     

Synthesis,characterization and crystal structure of one Cu(II) complex with flexible tetrapyridine and fatty acid ligand

One new title compound [Cu₂(TPOM)(adi)₂]_n · 4nH₂O (1) (TPOM = tetrakis(4-pyridyloxymethylene)methane, adi = adipic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction.     

Binuclear, 2D grid and 3D interlocking coordination polymers based on 1,2,4,5-benzenetetracarboxylic acid and 4,4′-azobispyridine

Three new nickel(II) complexes [Ni₂(btec)(azopy)₂(H₂O)₈]·2H₂O (1), {[Ni(H₂btec)(azopy)(H₂O)₂]·(azopy)}_n (2) and {[Ni₄(btec)₂(azopy)₃(H₂O)₁₀]·8H₂O}_n (3) (H₄btec = 1,2,4,5-benzenetetracarboxylic acid; azopy = 4,4′-azobispyridine) have been synthesized by tuning the reaction temperature and the metal–ligand ratio. They were characterized by single-crystal X-ray diffraction and elemental analysis. 1 shows a binuclear structure, 2 exhibits a 2D grid, and 3 features an interesting 3D framework with (6³)(4.6²)(4².6².8²) topology formed by two types of interlocked 2D layers.     

A novel three dimensional 3d–4f heterometallic coordination framework with 2, 2′-bipyridine-3-carboxylate and oxalate ligands

The 3D heterometallic polymeric complex 1 {[Nd₂Cu₂(L)₂ (OXA)₄·2(2H₂O)]·2(3H₂O)}_n (HL = 2, 2′-bipyridine-3-carboxyic acid, OXA = oxalate) was obtained from hydrothermal reaction of Nd₂O₃, Cu(ClO₄)₂, HL and oxalic acid in the presence of ethanol and water. X-ray single crystal diffraction investigation of the polymeric complexes {[Nd₂Cu₂(L)₂(OXA)₄·2(2H₂O)]·2(3H₂O)}_n exhibits an interesting and novel topological structure.     

A 3D Cu(II) coordination polymer constructed from BIBP (BIBP = 5,5′-bis(1H-imidazol-1-yl)-2,2′-bithiophene) ligand with semiconductive property

Hydrothermal reaction of Cu(NO₃)₂·3H₂O with BIBP and H₂hfipbb at 105 °C yielded a novel 3D Cu(II) coordination polymer, {[Cu₂(BIBP)_0.5(hfipbb)₂(CH₃CN)]·5H₂O}_n (1) [BIBP = 5,5′-bis(1H-imidazol-1-yl)-2,2′-bithiophene, H₂hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid)]. Compound 1 displays a 3D 2-fold interpenetrating framework with {4⁴.6⁶} sqp topology, containing interesting ⋯LRLR⋯ double helical chains. The compound 1 was characterized by IR spectra, elemental analysis, thermal analysis and single crystal X-ray diffraction. In addition, solid-state UV–vis spectra experiment shows that compound 1 exhibits semiconductive property with a band gap of 2.46 eV.     

Three-dimensional fourfold interpenetrated (10, 3)-b nickel(II) framework with 5-(isonicotinamido)isophthalate

A new three-dimensional nickel(II) metal-organic framework [Ni(INAIP)(H₂O)₂]_n · nH₂O (1) [H₂INAIP = 5-(isonicotinamido)isophthalic acid] was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray structure determination, thermogravimetric analysis, X-ray powder diffraction, IR and magnetic studies. The compound 1 has (10, 3)-b topology with not well known fourfold interpenetration, in which both Ni(II) atoms and INAIP^2? ligands act as three-connected nodes.     

Synthesis,characterization and crystal structure of one Mn(II) complex with 4,4′-bisimidazolylbiphenyl and 4,4′-sulfonyldibenzoic acid

One new title compound [Mn₃(BIBP)(sdb)(NO₂⁻)₂(H₂O)₂]_n·2DMF (1) (BIBP = 4,4′-bisimidazolylbiphenyl, sdb = 4,4′-sulfonyldibenzoic acid) has been synthesized under hydrothermal condition. The title compound was characterized by IR spectra, thermal analysis, single crystal and powder X-ray diffraction. Magnetic susceptibility measurements indicate that compound 1 exhibits antiferromagnetic coupling interaction.     

A novel three-dimensional coordination polymer containing tetranuclear [Co4(μ3-OH)2] building blocks: Synthesis,crystal structure and magnetic behavior of {[Co2(btc)(μ3-OH)(H2O)2] · H2O}n

A cobalt coordination polymer {[Co₂(btc)(μ₃-OH)(H₂O)₂] · H₂O}_n 1 (btc = 1,2,4-benzenetricarboxylate) was synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction method. In 1, the six-coordinated Co(II) ions are held together by two bridging hydroxides to form a tetranuclear [Co₄(μ₃-OH)₂] unit, which are connected further through btc³⁻ ligands in a new μ₇-bridging mode to give a porous three dimensional framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.     

A new 3D pillared-layer porous framework with intersecting open channels in the Co/triazolate/carboxylate system: Synthesis,structure and magnetism

A new Co(II) coordination polymer, namely [Co₆(btc)₄(dtb)₂(H₂O)₃]_n (1) (H₃btc = 1,3,5-benzenetricarboxylic acid, dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene), has been synthesized by combining the mixed ligands of H₃btc and dtb with Co(Ac)₂·4H₂O under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1 feature a 3D open framework with intersecting channels based on Co-btc^3 − layers and btc^3 − and dtb pillars. The magnetic property of the complex has also been investigated at room temperature.