Shan-Tang Yue

Syntheses, structures, and photoluminescent properties of a series of zinc(II)–3-amino-1,2,4-triazolate coordination polymers constructed by varying carboxylate anions

To explore the influence of different carboxylate ligands on the structures of metal–organic frameworks (MOFs), five novel Zn(II) coordination polymer compounds, namely, {[Zn(atz)(bia)]}n (1), {[Zn3(atz)3(tpa)3/2]}n (2), {[Zn2(atz)2(pda)]}n (3), {[Zn4(atz)2(btc)]·4H2O}n (4) and {[Zn2(atz)2(btec)]·H2O}n (5) have been successfully obtained by introducing various secondary auxiliary ligands in Zn(II)–L systems, characterized by elemental analysis, FT-IR, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction (Hatz = 3-amino-1,2,4-triazolate, Hbia = benzoic acid, H2tpa = 1,4-terephthalic acid, H2pda = 1,4-benzenediacetic acid, H3btc = 1,3,5-benzenetricarboxylate, H4btec = 1,2,4,5-benzenetetracarboxylic). Compound 1 features a 2D layer with (4.82) topology, which is further stabilized by hydrogen bonds between the uncoordinated amino groups and uncoordinated oxygen atoms from bia ligands. Compound 2 exhibits a 3D 3,4-connected framework with {4.82.103}{4.82} topology, constructed from Zn(II) ions and μ3-atz ligand. Compound 3 displays a 3D 3,4-connected network with {4.6.8}{4.62.83} topology. Compound 4 possesses a 3D 9-nodal network with a point symbol of {4.8.9}2{4.82}{4.83.9.10}{5.8.9}4{5.82}. Compound 5 shows a 3D 3,4,4-connected framework with {4.82}4{42.83.10}2{84.102} topology. The diverse structures of these five complexes demonstrate that the skeleton of carboxylate ligands have a significant impact on the construction of MOFs. Moreover, the luminescence properties of complexes 1–5 were investigated in the solid state.

A series of novel 2D heterometallic 3d–4f heptanuclear complexes based on the linkages of Ln2(ina)6 chains and [Cu(CN)] chains

Five novel 2D heterometallic coordination polymers, Ln2Cu5(ina)6(CN)5.5·4H2O [Ln = Nd (1), Eu (2), Tb (3), Gd (4), Sm (5); ina = isonicotinic acid], have been synthesized under hydrothermal conditions and characterized by elemental, infrared, thermogravimetric and X-ray diffraction analyses. These complexes are constructed of Ln2(ina)6 chains, Cu–CN–Cu, and CN–Cu–CN chains, which represent the first examples of 3D coordination compounds created by using a combination of metal–cyanide chains, lanthanide–carboxylate linear chains and O–H⋯N hydrogen bonds.

A new family of 3D heterometallic 3d–4f organodisulfonate complexes based on the linkages of 2D [Ln(nds)(H2O)]+ layers and [Cu(ina)2]− chains

Seven novel 3D heterometallic coordination compounds, LnCu(nds)(ina)2·H2O [Ln = Eu (1), Ce (2), Er (3), Gd (4), Sm (5), Tb(6), Dy(7); nds = 2,6-naphthanlenedisulfonate; ina = isonicotinic acid], have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectra, thermogravimetric analysis and single-crystal X-ray diffraction analysis. These compounds are isostructural and constructed by the linkages of 2D [Ln(nds)(H2O)]+ layers and Cu(ina)2− chains, which represent the first examples of 3D heterometallic coordination polymers created by the organodisulfonate ligands. Moreover, the complexes exhibit a novel (3,6)-connected net. The luminescence properties of complexes 1, 5 and 6 and the magnetic property of 4 were also investigated.

Novel three-dimensional Ln–Ag 4d–4f heteropentametallic helix-based microporous metal–organic framework with unprecedented (3,4,5,6)-connected topology constructed from isonicotinate ligand

An unprecedented 4d–4f heterometallic helix-based MMOF with a new (3,4,5,6)-connected topology, {[Ln2Ag3(ina)6(ox)0.5(μ2-OH2)(H2O)2.5]·1.5H2O·2NO3}n, is presented, which consists of coaxial bi-strand helices interconnected by the carboxyl groups of the ligands. Selective anion-exchange functions of the title compound containing NO3− counter anions were identified.

Series of novel 3D microporous heterometallic 3d–4f coordination frameworks with (5,6)-connected topology: synthesis, crystal structure and magnetic properties

The hydrothermal reaction of rare earth nitrates, CuCN, 1H-1,2,3-triazole-4,5-dicarboxylic acid (H3tda), and isonicotinic acid (Hina) resulted in the formation of a new series of 3d–4f heterometallic coordination polymers [LnCu(tda)(ina)2(H2O)]·3H2O (Ln = Eu (1), Tb (2), Gd (3), Dy (4), Ho (5)], H3tda = 1H-1,2,3-triazole-4,5-dicarboxylic acid, Hina = isonicotinic acid). Complexes 1–5 are isostructural and structurally characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis reveals that the metal cations in these compounds are firstly interconnected by H3tda ligands to produce a carpet-shaped heterometallic ring [Ln2(tda)2Cu4], and then pillared by bridging Hina molecules to form the 3D layer-pillared porous Ln(III)–Cu(II) heterometallic coordination polymers. In addition, the magnetic properties of 1–5 were also investigated in detail.

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6(COO)6] (H2O)6} and {Ho2[C6(COO)6](H2O)6}

Abstract Two novel 3-D coordination compounds, Nd2[C6(COO)6](H2O)6 (1) and Ho2[C6(COO)6](H2O)6 (2), were hydrothermally synthesized from mellitic acid and neodymium perchlorate (or holmium perchlorate) in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 (4) nm, b=0.6687 (2) nm, c=1.0224(3) nm, V=0.92523(5) nm3, Z=4, D=2.630 g/cm3, F(000)=696.0, Goof=1.052. Final R indices [I >2Σ(I)]: R1=0.0195, wR2=0.0382 for 1; a=1.3411(2) nm, b=0.6586(1) nm, c=1.0116(2) nm, V=0.8935(3) nm3, Z=4, D=2.877 g/cm3, F(000)=724.0, Goof=1.061. Final R indices [I >2Σ(I)]: R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.

Syntheses, crystal structures, and luminescence of carboxylato-bridged coordination compounds

Two 2-D metal carboxylate coordination compounds [Tb(pydc)(ox)1/2(H2O)2] (1) and [Cd(pydc)(me)(H2O)]2 · H2O (2) (pyridine-2,5-dicarboxylic acid = pydc, oxalic acid = ox, me = methanol) have been synthesized under hydrothermal conditions. Carboxylates are building blocks in the formation of zigzag chain and cockle stair-like chain structures for 1 and 2, respectively. Both the compounds have been structurally determined by single-crystal X-ray diffraction, and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and fluorescence spectra.

One new lanthanide complex with mixed sulfate and oxalate ligands: hydrothermal synthesis, crystal structure, and magnetic properties

A new lanthanide complex K[Gd(ox)(SO4)(H2O)] (1) with sulfate and oxalate ligands has been synthesized under hydrothermal conditions. The compound crystallizes in the monoclinic space group P21/c with a = 6.5849(1) Å, b = 8.5660(1) Å, c = 14.7660(2) Å, β = 112.470(1)°, C2H2GdKO9S, M = 398.46, Z = 4, V = 769.66(2) Å3, F(000) = 740, R 1 = 0.0199 and ωR = 0.0514. The solid-state DC magnetic susceptibility measurements of 1 revealed antiferromagnetic behavior with an S = 7/2 ground spin state.

Coordination complexes based on V-shaped ligand and rare earth(III) ions: lanthanide contraction effect induced structural changes

A series of metal-organic frameworks, {Ln2(SDB)3(H2O)5}n [Ln = Eu(1), Gd(2), Tb(3), Dy(4)], {[Ln2(SDB)3(H2O)4]·H2O}n [Ln = Ho(5), Er(6), Tm(7), Y(8)] and {[Lu2(SDB)3·(H2O)3]·4H2O}n (9) (H2SDB = 4,4’-sulfonyldibenzoic acid), have been synthesized under hydrothermal conditions by using the V-shaped ligand H2SDB. The structures of the complexes have been determined by single-crystal X-ray diffraction and further characterized using IR spectroscopy, powder X-ray diffraction, and thermogravimetric analysis. The single crystal X-ray structures show that 1–4 are isostructural featuring a 2-D weaving structure based on two chain structures containing binuclear units and organic linkers. The structures of 5–8 are analogous to those of 1–4 except that they contain coordinated solvent. Complex 9 forms a 1-D structure containing binuclear units connected by organic linkers. This series affords an opportunity to study the effect of lanthanide contraction, demonstrating that the average C–S–C bond angle in coordinated H2SDB decreases as the atomic number increases. The luminescence of 1 and 3 are also reported.

Construction of a porous Na–Cd mixed metal–organic framework based on biphenyl-4,4′-dicarboxylate and benzotriazole

A novel mixed metal–organic framework, 2H3O·[NaCd3(C14H8O4)3(C6H4N3)3]·5.5H2O, has been synthesized under solvothermal conditions and characterized by single-crystal X-ray structure determination, IR spectroscopy, elemental analysis, TGA, and powder X-ray diffraction. Crystal structure analysis shows that the complex is a 3D framework with hexagonal channels accommodating guest water molecules. Furthermore, the photoluminescence properties and nitrogen gas adsorption of this complex were investigated. The complex exhibits strong photoluminescence emission, and its open cavities possess nitrogen adsorptive ability.Graphical abstract