Jin-Sheng Gao

A new topology constructed from an octamolybdate and metallomacrocycle coordination complex

A novel complex, [CuI2L2]2[Mo8O26] (1), was hydrothermally synthesized by using ammonium molybdate, copper nitrate and 1,3-bis(imidazol-l-yl-methyl)benzene. Complex 1 exhibits a new 3D (3,4,6)-connected topological structure with a Schlafli symbol of (4·6·8)2(42·64·83·102·123)(44·62)2, which is constructed by [Mo8O26]4− anions linking a [4 + 4] metallomacrocycle.

Construction of two interpenetrating coordination networks based on 4,4′-bis(1H-imidazol-1-yl-methyl)biphenyl and effect of carboxylic acids

To investigate the construction of interpenetrating coordination networks and the effect of ligands, [Zn(bimb)(bdc)]·H2O (1) and [Zn(bimb)(Hbtc)]·H2O (2) [bimb = 4,4′-bis(1H-imidazol-1-yl-methyl)biphenyl; H2bdc = 1,2-benzenedicarboxylic acid; H3btc = 1,3,5-benzenetricarboxylic acid] were hydrothermally synthesized and characterized by elemental analysis, IR spectra, Powder X-ray diffraction, and thermogravimetric analysis. Complex 1 shows a 3-D uoc type topology with twofold interpenetration. However, 2 exhibits a different 2-D self-penetrating network owing to hydrogen bonds of Hbtc between the two interpenetrating sql sheets, indicating that different carboxylic ligands could affect the interpenetration structures. Photoluminescence of bimb and the two complexes are also studied. Graphical Abstract Effect of H2bdc and H3btc as different mixed ligand on the structures of zinc coordination polymers based on bimb.

Two cationic [(CuxIy)x−y]n motif based coordination polymers and their photocatalytic properties

Cuprous iodide (CuI)-based coordination compounds with the general chemical formula of CuI(L) are well-known for their structural diversity and strong photoluminescence and are therefore considered as promising candidates for a number of optical applications. Reported here are two cuprous iodide coordination polymers (CPs), {[Cu3I2TBA]·H2O}n (1) and {[Cu2I(HTBA)TBA]·2H2O}n (2) (HTBA = 4-(4H-1,2,4-triazol-4-yl)benzoic acid). Structures of CPs 1 and 2 are determined by single crystal X-ray diffraction and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. CPs 1 and 2 with a significant feature of novel cationic [(CuxIy)x−y]n motifs are synthesized under controlled reaction conditions via adopting HTBA as ligand. CP 1 displays a 3,6-connected net, while CP 2 shows a coordination chain. Further, the catalytic properties of CPs 1 and 2 are investigated in the degradation of methyl blue.

Synthesis, structures, luminescence and magnetism of nine lanthanide complexes with three-dimensional frameworks constructed from 2-(pyridyl-N-oxide)methylphosphonic acid and oxalic acid

To investigate the coordination nature of the pyridyl-N-oxide phosphonate ligands with rare earth metals, two series of nine lanthanide complexes, namely, {[Ln(HL)((C2O4)0.5)2(H2O)]·3H2O}n {Ln = Eu(1), Gd(2), Tb(3), Dy(4) and Ho(5)} and {[Ln2(L)(C2O4)2(H2O)3]·H2O}n {Ln = Er(6), Tm(7), Yb(8) and Lu(9)} {H2L = 2-(pyridyl-N-oxide)methylphosphonic acid; H2C2O4 = oxalic acid }, have been hydrothermally synthesized and characterized by IR spectroscopy, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. Complexes 1–5 are isomorphic, featuring a three-dimensional (3D) porous structure with a dia topological framework, while the isomorphic complexes 6–9 show a 3D 3,4-connected topological framework with a point symbol of {72·8}2{73·83}. Photoluminescence spectra of complexes 1 and 3 exhibit the strong luminescence characteristic of Eu(III) and Tb(III) ions, respectively, suggesting that HL− and L2− anions are able to efficiently sensitize the luminescence of lanthanide ions. The magnetic analyses of complexes 2–5 show the characteristic magnetic susceptibilities of isolated Gd(III), Tb(III), Dy(III) and Ho(III) ions, respectively.

Syntheses and properties of two chiral multidentate carboxylate copper coordination compounds

A chiral ligand, (R)-2-(4-(carboxymethoxy)phenoxy)propanoic acid, is employed as building block to construct two chiral coordination compounds, [Cu(L)(bipy)(H2O)] (1) and [Cu2(L)2(phen)4(H2O)13] (2), by the solvent-thermal method and the volatilization method, respectively. The compounds are characterized by single-crystal X-ray diffraction (XRD), IR spectra, XRD, TGA, and circular dichroism spectra. Compound 1 is comprised of right-handed helical chains and 2 shows a separated structure, both of which extend to 3-D supramolecular framework by hydrogen bonds and π ··· π interactions. CD indicates both compounds retain original stereo character with strong fluorescence at room temperature.

pH-dependent syntheses, luminescence and magnetic properties of two-dimensional framework lanthanide 1,3-diarylphosphonate complexes

A series of novel organic–inorganic complexes based on trivalent lanthanides and 1,3-C6H4[CH2P(O)(OH)2]2 (H4L) formulated as Ln(HL)(H2O)2 (Ln = La, 1; Pr, 2; Nd, 3; Sm, 4; Eu, 5; Gd, 6; and Tb, 7) have been obtained as single phases by regulating the pH under hydrothermal conditions. Complexes are isostructural and feature a network in which the LnO7 polyhedra are interconnected by bridging CPO3 tetrahedra into inorganic layers. These layers are further stacked with the benzyl groups of ligands via C–H⋯π interaction into a laminar framework architecture. Luminescent measurements indicate that complexes 4, 5 and 7 show strong metal-centered emission bands in yellow, red and green light regions, respectively. Magnetic properties of 2 and 7 have also been studied.

Ligand-induced isomerization: from 3D to 2D→3D POMOFs constructed from silicotungstate anions, Cu(I) and 1,n-di(4H-1,2,4-triazol-4-yl)benzene (n = 3, 4) ligands

Two novel POMOFs, [Cu4(1,3-dtzb)4(SiW12O40)]n (1) and [Cu4(1,4-dtzb)4(SiW12O40)]n (2), based on Keggin-type polyoxometalates have been hydrothermally synthesized by altering organic ligands {1,n-di(4H-1,2,4-triazol-4-yl)benzene: n = 3 (1,3-dtzb) and 4 (1,4-dtzb)}. In POMOF 1 constructed from the V-shaped 1,3-dtzb meta-ligand, the ligands link the Cu(I) ions to form a 20-member metallomacrocycle with [Cu2(1,3-dtzb)2] as the SBU, four of which assemble into a cage-like [Cu2(1,3-dtzb)2]4 motif to embed the POM anion, resulting in a 3D POMOF showing a new type of topological structure with a point symbol of {4·53·72}{52·8}. However, when the ligand is changed to the 1,4-dtzb straight para-ligand, POMOF 2 with a different structure is achieved. The ligands link the Cu(I) ions into a basic 3,3-connected net, and then the POM anions insert into the space between two adjacent nets to form a POM-pillared double-layer framework. The large cavities of the POM-pillared double layers allow the occurrence of an interpenetrated 2D→3D framework. The cyclic voltammetric behavior and photocatalytic properties of POMOFs 1 and 2 were also investigated.

Syntheses, structures, and characterizations of three Ag(I) complexes constructed by length-modulated pyrazole-based ligands

Three coordination complexes with N-donor ligands, Ag2(L1)1.5(NO3)2 (1), Ag3(L2)2(NO3)3 (2), and Ag(L1)2NO3 (3) {L1 = 1,4-bis(pyrazole-1-ylmethyl)benzene, L2 = 4,4′-bis(pyrazole-1-ylmethyl)biphenyl}, have been synthesized and structurally characterized by elemental analysis, IR spectroscopy, TGA, and X-ray single crystal diffraction. Complex 1 shows a 3-D fsh-3,4-P21/c structure with brevity code {83}2{85·10}. Complex 2 has a 3-D framework with a 2-D layer penetrated by an infinite 1-D zigzag chain. Complex 3 exhibits a (4,4)-net racemizing layer structure with nitrate anions filling the cavity. The results indicate that L1 and L2 can adopt varied conformations in formation of the complexes, and the length of the ligands plays a key role in configuring and directing the corresponding structure of the complexes.

1,1'-(Butane-1,4-di-yl)diimidazole-3,3'-diium tetra-chloridozincate(II) dihydrate.

In the title compound, (C10H16N4)[ZnCl4]·2H2O, the cation lies abouton a center of inversion and the anion about a twofold rotation axis. The ZnII atom is four-coordinate in a tetrahedral environment. The cations, anions and water molecules are linked by N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds into a two-dimensional network.

[1,2-Bis(2-pyridyl-meth-oxy)benzene-κN,O,O',N']bis-(nitrato-κO)copper(II).

In the title compound, [Cu(NO3)2(C18H16N2O2)], the CuII ion is six-coordinated in a Jahn–Teller-distorted octahedral environment defined by two O and two N atoms from the ligand and two O atoms from two monodentate nitrate anions.