A new 2D 5-connected coordination polymer based on 3,4-bis(pyridin-4-ylmethoxy)benzoic acid ligand

A new 2D 5-connected coordination polymer [Zn₃(HL²)(1,4-bdc)₃] (1) (HL² = 3,4-bis(pyridin-4-ylmethoxy)benzoic acid, 1,4-H₂bdc = 1,4-benzenedicarboxylate) has been hydrothermally constructed using HL², 1,4-bdc ligands as linear linkers and Zn₃-clusters as 5-connected nodes. In addition, powder X-ray diffraction, photoluminescent property and thermogravimetric analysis for 1 are investigated in detail.     

An unprecedented ten-connected 3D metal–organic framework based on hexanuclear cobalt(II) cluster building blocks

A 3D metal–organic framework (MOF), [Co₃(μ₃-OH)(μ₂-H₂O)(BPT)(HBPT)(DMF)₂]·(DMF)(H₂O) (1) (DMF = N, N′-dimethylformamide) has been synthesized by self-assembly of cobalt(II) oxide and biphenyl-3, 4′, 5-tricarboxylate (H₃BPT) under solvothermal reaction. Compound 1 displays unique (2,3,10)-connected trinodal connected topology. Besides, 1 represents a rare example of MOF possessing free carboxylic acids. In addition, the magnetic property of the compound is investigated.     

Two transition metal coordination polymers constructed from 1,4-naphthalenedicarboxylate and N/O-donor auxiliary ligands: Syntheses,structures and magnetic property

Two transition metal coordination polymers (CPs), namely, Cd(1,4-NDC)(py) (1), Co₂(1,4-NDC)₂(DMF)₂ (2) (1,4-NDCH₂ = 1,4-naphthalenedicarboxylic acid, py = pyridine, DMF = N,N-dimethylformamide) have been synthesized and characterized. Compound 1 contains one-dimensional chains, which are further linked by the NDC^2 − ligands to form a three-dimensional framework with a 5,5T2 topology network. There exist two types of left-hand helical chains interconnected to each other through the Cd(II) center in compound 1. Although compound 2 has been reported previously, in this work the synthetic method of 2 is modified to obtain high quality crystals. In addition, the magnetic property of compound 2 is investigated, which shows the metamagnetic behavior induced by the external field.     

Construction of a new 3D Zn(II) coordination polymer with (4,6)-connected topology: Synthesis,structure and luminescence

A new coordination polymer of {[Zn₂(odpa)(IP)]·4H₂O}_n (1) (H₄odpa = 3,3′,4,4′-oxydiphthalic acid and IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline), is reported. The 3D (4,6)-connected {4⁴∙6²∙8⁸∙12}{4⁴∙6²} topology net is formed by IP and odpa ligands in 1. Interestingly, the IP ligand acts as a tridentate mode and extends the resulting 3D feature. The luminescence study indicates that the title compound emits bright red fluorescence.     

A three-dimensional (3,4)-connected network of 658 topology containing hexagonal channels constructed from cadmium(II) and 5-aminoisophthalate

The hydrothermal reaction of H₂aip (aip²⁻=5-aminoisophthalate) and Cd(II) acetate dihydrate yields an unprecedented three-dimensional (3,4)-connected network, [Cd(aip)(H₂O)] · H₂O, with 6⁵8 topology and interesting photoluminescent behaviour in the solid state.     

A Ni(II) ferromagnet with mixed pyridine-3,5-dicarboxylate-1,4-bis(imidazol-l-yl)butane heterobridges exhibiting long-range ordering and hysteresis loop

A rare Ni-ferromagnet [Ni(pdc)(bib)]·2H₂O (H₂pdc = pyridine-3,5-dicarboxylic acid, bib = 1,4-bis (imidazol-l-yl)butane) has been prepared, which possesses a 3D supramolecular network based on (3,5)-connected helical-armed 2D layers. Interestingly, at high temperature (> 12.7 K), 1 exhibits a weak ferromagnetism, whereas at low temperature, it shows unusual long-range ordering (LRO) behaviors combining spin canting and hysteresis loop.     

Blue-green photoluminescent 5- and 10-connected metal 5-(4′-carboxy-phenyl)tetrazolate coordination polymers

Hydrothermal reaction of Zn/Cd salts, NaN₃ and 4-cyanobenzoic acid via in situ [2 + 3] cycloaddition generated two blue-green photoluminescent coordination polymers [Zn(cptta)(H₂O)] (1) and [Cd(cptta)(H₂O)] (2) (H₂cptta = 5-(4′-carboxy-phenyl)tetrazole). When only metal ions are considered as nodes, 1 shows rare 5-connected Shubnikov plane topological type and 2 has unprecedented 10-connected {3¹².4²⁴.5⁹} topological type.     

Syntheses and structures of cadmium(II) and cobalt(II) coordination polymers based on 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) and carboxylate ligands

Two novel coordination polymers containing Cd(II) and Co(II) metals, connected via 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) (L) ligand, have been synthesized. Compound [Cd(L)₂(p-BDC)] · 2H₂O (1) (p-BDC = 1,4-benzenedicarboxylate anion) is a three-dimensional interdigitated supramolecular architecture. Compound [Co(L)(BTCA)_0.5] (2) (BTCA = 1,2,3,4-butanetetracarboxylate anion) possesses a unique (3,4)-connected 3D framework with (8³)₂(8⁵ · 10) topology.     

A new 3D cobalt(II) complex with left- and right-handed helical channels

A new 3D complex, {[Co(btec)_0.5(imb)(H₂O)]∙1.5H₂O}_n (1) (imb = 2-(1H-imidazol-1-methyl)-1H-benzimidazole, H₄btec = 1,2,4,5-benzenetetracarboxylic acid) has been synthesized by solvothermal technique. X-Ray diffraction analysis indicates that complex 1 displays a 3D framework with left- and right-handed helical channels and very high porous, which can be simplified as a 4,4,4-connected 3D topology with a Schläfli symbol of (3² · 10³ · 11)(3² · 10⁴)(3² · 10³ · 11). Moreover, its IR spectra, PXRD patterns, thermogravimetric curves, and luminescent emissions were studied at room temperature.     

Two different Zn(II) interpenetrating networks derived from different dicarboxylate ligands mixed with a flexible imidazole-based ligand

Two interpenetrating networks based on 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (bmimx), namely, {[Zn₂(bmimx)₂(cba)₂]·2.5H₂O}_n (1) and {[Zn(bmimx)(suc)]·2H₂O}_n (2) (H₂cba = 4,4′-carbonyldibenzoic acid, H₂suc = succinic acid) have been prepared at hydrothermal condition by varying the dicarboxylate ligands. Single-crystal X-ray diffraction indicates that complex 1 shows a 4-connected dmp net with 3-fold interpenetration which contains 1D (Zn − cba)_n right- and left-handed helical chains; complex 2 shows a dia topology with 4-fold interpenetration. The results indicate that the spacers of dicarboxylate coligands have an important effect on the interpenetrating characters and ultimate frameworks. Moreover, the photoluminescence properties of the two complexes were studied in the solid state at room temperature.     

An effective approach for constructing acentric heterometallic-organic framework with catalytic activity

A new acentric heterometallic–organic framework, [CdMg (btec)(DMF)(H₂O)₃] (1) (H₄btec = 1,2,4,5-benzene tetracarboxylic acid), has been solvothermally synthesized. It features a 4-connected net with typical pts topology. To the best of our knowledge, compound 1 is the first example of Cd–Mg heterometallic organic framework based on the H₄btec ligand. Compound 1 has potential unsaturated metal sites after the removal of coordination water molecules, so it shows good catalytic activity on the diethylzinc addition to benzaldehyde. The photoluminescent property of 1 is also investigated.     

A lead(II)-orotate coordination polymer with a new coordination mode: Synthesis,structure and luminescent property

A lead(II) orotate complex [Pb(HOr)(H₂O)]_n (1), (H₃Or = orotic acid) was synthesized under hydrothermal condition and characterized by X-ray diffraction, IR, solid-state photoluminescence and thermogravimetric analysis. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (4⁸, 6⁶, 8)(4¹³, 6²) topology. The complex exhibits photoluminescence at 546 nm (λ_ex = 350 nm).     

Two new luminescent Cd(II)/Zn(II) metal–organic frameworks for exceptionally selective detection of picric acid explosives

Two new coordination polymers, {[Cd(BIDPT)(oba)]·0.5H₂O}_n (1) and {[Zn(BIDPT)(4,4′-sdb)]·2.25H₂O}_n (2) (BIDPT = 4,4′-bis(imidazol-l-yl)diphenyl thioether, H₂oba = 4,4′-oxydibenzoic acid, 4,4′-H₂sdb = 4,4′-sulfonyldibenzoic acid), have been solvothermally synthesized and characterized. Both 1 and 2 show 2-fold interpenetrating 3D frameworks with {6⁵ ∙ 8} cds and {6⁶} dia topology, respectively. These two coordination polymers show strong luminescence and their luminescence could be quenched by a series of nitro explosives. Importantly, they exhibit very highly sensitive and selective detection of picric acid compared to other nitro explosives.     

A new self-penetrating amine-decorated microporous metal–organic framework: Crystal structure,adsorption selectivity,and luminescence properties

A new microporous metal–organic framework, [Cd(bpdc)_0.5(atz)(DMF)]·0.5DMF (1) (H₂bpdc = 4,4′-biphenyldicarboxylic acid, Hatz = 3-amino-1,2,4-triazole, DMF = N,N-dimethylformamide) has been solvothermally synthesized by employing the mixed H₂bpdc and Hatz ligands. 1 is a 3D pillared-layer framework, consisting of Cd–triazolate layer and dicarboxylate pillar, which exhibits a 6-connected (4⁶ · 6⁸ · 8) self-penetrating net. Because of the pore system functionalized by amino groups and open metal sites, this material shows high CO₂ adsorption selectivity over H₂ and N₂. In addition, 1 exhibits blue emission at ambient temperature.     

Metal ions directed self-assembly based on rigid polycarboxylate ligand 5-tert-butyl isophthalic acid and flexible N-heterocyclic ligand 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene

Two new complexes {[Cd(bmimx)_0.5(tbip)(H₂O)] · H₂O}_n (1) and [Zn(bmimx)(tbip)]_n (2) (bmimx = 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, H₂tbip = 5-tert-butyl isophthalic acid) based on mixed ligands have been hydrothermally synthesized by varying the metal ions. Structural analysis reveals that complex 1 displays a 2D layer structure with a 4⁴-sql topology; complex 2 exhibits a 3D 4-fold interpenetrated framework with sra topology. The structural differences between 1 and 2 indicate that metal ions have significant effects on the formation of the final architectures. In addition, the thermal stabilities and photoluminescent properties of the two complexes were also investigated.     

Solvent-induced 1- and 2-D Cd(II) coordination polymers based on a bent polypyridyl ligand

Two Cd(II)-tppda (tppda = N,N,N′,N′-tetrakis(2-pyridyl)-2,6-pyridinediamine) coordination polymers have been prepared via variations of the templating solvent. The solvated complex [Cd₂(tppda)(DMF)₂(μ-SCN)₂(SCN)₂]_n (1) exhibits a 1-D pseudo-helical structure, whereas the unsolvated complex [Cd₂(tppda)(μ-SCN)₄]_n (2) features a 2-D metal-organic framework (MOF). Both are luminescent in the solid state, with emission maxima 444 and 435 nm for 1 and 2, respectively.     

Construction and photoluminescence properties of two novel zinc(II) and cadmium(II) benzyl-tetrazole coordination polymers

Two new d¹⁰ coordination polymers, Zn(Beta)₂ (1) and Cd₂(Beta)₃Cl(H₂O) (2) (Hbeta = 5-benzyl-tetrazole) have been synthesized by the in situ [3 + 2] cycloaddition reaction of 5-benzylacetonitrile, sodium azide and MCl₂ [M = Zn (1); M = Cd (2)] under hydrothermal condition. Complex 1 is a coordination polymer comprised of numerous mildly undulated two-dimensional (2D) layers with a (4, 4) topological network; while complex 2 is a 3D coordination framework constructed from the interconnection of various helical chains through cadmium–chlorine bridges. Furthermore, the luminescence properties of two complexes have been investigated.     

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.     

Solvent directed assembly of two zinc(II)-2-(4-pyridyl)-4,5-imidazoledicarboxylate frameworks

Two zinc(II)-2-(4-pyridyl)-4,5-imidazoledicarboxylate frameworks, formulated as {[Zn₃(HPIDC)₃(DMF)₂](DMF)₂(H₂O)₂}_n (1) and {[Zn₄(HPIDC)₄(DMF)₄](DMF)₂(FMA)₂(H₂O)}_n (2) (H₃PIDC = 2-(4-pyridyl)-1H-4,5-imidazoledicarboxylic acid, DMF = N,N′-dimethylformamide, FMA = formamide) have been solvothermally synthesized depending on whatever solvents are used. In both structures, the HPIDC^2 − anions act as tripodal connectors to chelating with three zinc(II) cations while the zinc(II) cations coordinate with three HPIDC^2 − anions, to form the T-shape molecular building blocks [Zn_n(HPIDC)_n], which further connect in interdigitating or alternating fashion to result in the assembly of two different 3,3-connected networks. The luminescence behaviors and solvent effect were also discussed.     

3D PbII-coordination framework based on rod-shaped Pb–O–Pb SBUs defining a new (4,5)-connected net topology

A novel 3D coordination framework [Pb₂(hfipbb)₂(bpp)]_n (1) [H₂hfipbb = 4,4′-(hexa-fluoroisopropylidene)bis(benzoic acid), bpp = 1,3-bis(4-pyridyl)propane] based on inorganic rod-shaped infinite Pb–O–Pb chain is presented, which possesses a new (4,5)-connected network topology and shows high thermal stability and strong photoluminescence at room temperature.