Yun-Liang Jiang

Novel Noncentrosymmetric Zinc Coordination Polymer Containing an Unusual Zinc Carboxylate-Sulfonate Substructure with a (10,3)-d Topology and Its Second-Harmonic-Generation Properties

A novel 3D coordination polymer, Zn(2)(μ(2)-OH)(SIP)(DPP) (1), with mixed ligands of 5-sulfoisophthalate (SIP) and 1,3-di-4-pyridylpropane (DPP), has been hydrothermally synthesized and characterized. 1 contains an unusual 3D subnet with distorted (10,3)-d topology and left/right-handed helical channels. Second-harmonic-generation (SHG) measurements revealed that the material has a strong SHG response (∼2.5 times that of potassium dihydrogen phosphate (KDP)) and is phase-matchable. In addition, photoluminescent and thermogravimetric analysis were also performed on 1.

Diversity of lanthanide(III)-2,5-dihydroxy-1,4-benzenedicarboxylate extended frameworks: syntheses, structures, and magnetic properties.

Six lanthanide(III)-2,5-dihydroxy-1,4-benzenedicarboxylate frameworks, namely, [Ln(H(2)-DHBDC)(1.5)(H(2)O)(2)](n) (Ln = La (1) and Pr (2); H(4)-DHBDC = 2,5-dihydroxy-1,4-benzenedicarboxylic acid), {[Nd(H(2)-DHBDC)(1.5)(H(2)O)(3)](H(2)O)}(n) (3), {[Eu(H(2)-DHBDC)(NO(3))(H(2)O)(4)](H(2)O)(2)}(n) (4), and {[Ln(2)(H(2)-DHBDC)(2)(DHBDC)(0.5)(H(2)O)(3)](H(2)O)(4)}(n) (Ln = Gd (5) and Dy (6)), with four different structural types ranging from 1D chain, 2D layer to 3D networks have been synthesized and structurally characterized. Compounds La (1) and Pr (2) are isomorphous and exhibit 3D frameworks with the unique 1D tubular channels. Compounds Nd (3) and Eu (4) are 2D layer and 1D zigzag chain, respectively, which are further extended to 3D supramolecular frameworks through extensive hydrogen bonds. Isomorphous compounds of Gd (5) and Dy (6) are 3D frameworks constructed from secondary infinite rod-shaped metal-carboxylate/hydroxyl building blocks. While the hydroxyl groups as secondary functional groups in the 1D chain of Eu (4) and 2D layer of Nd (3) are not bonded to the lanthanide centers, the hydroxyl groups in the 3D frameworks of La (1), Pr (2), Gd (5), and Dy (6) participate in coordinating to lanthanide centers and thus modify the structural types of theses compounds. The magnetic data of compounds Pr (2), Nd (3), Gd (5), and Dy (6) have been investigated in detail. In addition, elemental analysis, IR spectra, powder X-ray diffraction (PXRD) patterns and thermogravimetric analysis of these compounds are described.

A series of three-dimensional lanthanide(III) coordination polymers of 2,5-dihydroxy-1,4-benzenedicarboxylic acid based on dinuclear lanthanide units

The reactions of Ln(NO3)3 with 2,5-dihydroxy-1,4-benzenedicarboxylic acid (H2-DHBDC) under solvothermal conditions produce a series of isomorphous lanthanide coordination polymers with the empirical formula {[Ln2(DHBDC)3(DMF)4](DMF)2}n (Ln = La(1), Nd(2), Sm(3), Gd(4), and Er(5)). Compound {[Ln2(DHBDC)3(DMF)4](DMF)2}n contains dinuclear Ln2(COO)6 units, which are linked by the –C6H2(OH)2– spacers to form a three-dimensional framework exhibiting α-Po topology (pcu-(412·63) net) based on dinuclear Ln2(COO)6 nodes. The three-dimensional framework shows one-dimensional open channels that accommodate the coordinated and guest DMF molecules. Gas adsorption measurements on compound 4 indicate that the desolvated solid of 4 adsorbs CO2 and shows nonporous behavior toward N2. The adsorption favoring CO2 over N2 may arise from the chemical environments of the host framework, which contains the polar –OH groups of the phenyl and the π-electrons of the ligands. Magnetic measurements on compound 4 indicate that there is an antiferromagnetic interaction between Gd3+ ions.

Metal oxo cluster-based coordination polymers with rigid 1,4-naphthalenedicarboxylate and semirigid 1,3-di(4-pyridyl)propane ligands: syntheses, structural topologies, and luminescent properties

Hydrothermal reactions of Zn(NO3)2 or Pb(NO3)2 with 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) and 1,3-di(4-pyridyl)propane (dpp) lead to two novel metal oxo cluster-based coordination polymers, namely, [Zn5(μ3-OH)2(1,4-ndc)4(dpp)2]n (1) and [Pb5(μ4-O)(1,4-ndc)4(dpp)]n (2). The structures exhibit different cluster motifs depending on the nature of the metal ions. Compound 1 features a 3D structure based on the pentanuclear [Zn5(μ3-OH)2] secondary building unit (SBU) where the five zinc atoms are coplanar; its topological structure is an uninodal 10-connected network of (36.434.53.62) topology. The zinc ions in 1 have a coordination number varying from 4 to 6 and are accompanied by a variety of coordination geometries such as tetrahedral, trigonal bipyramidal, and octahedral. Compound 2 has a 3D architecture containing an unusual hexanuclear [Pb6(μ4-O)2] cluster unit composed of two edge-sharing oxygen-centred [Pb4(μ4-O)] tetrahedrons. One explanation for the presence of the centred bridging oxide ligands in 2 is that owing to steric constraints sufficient carboxylate ligands cannot coordinate to the Pb(II) centers to satisfy the positive charges of the Pb(II) cations. The Pb(II) ions in 2 exhibit diverse hemidirected coordination geometries with coordination numbers of 6 and 7. In the solid state, compounds 1 and 2 exhibit photoluminescence with emission maximum at 495 and 420 nm, respectively.

Syntheses, structures and properties of coordination polymers of cadmium(II) with 4-methyl-1,2,4-triazole-3-thiol ligand

Hydro(solvo)thermal reactions of cadmium(II) salts with 4-methyl-1,2,4-triazole-3-thiol (Hmptrz) afforded six novel cadmium(II) coordination polymers, namely, [Cd(mptrz)2]n (1), [Cd(mptrz)X]n (X = Br (2) and I (3)), [Cd(mptrz)(μ2-X)]n (X = Br (4) and Cl (5)), and [Cd3(μ3-OH)2(mptrz)4]n (6). Compound 1 is a 1D looped chain structure. Compounds 2 and 3 are isostructural and have 1D ladder structures. Compounds 4 and 5 are isomorphs and feature 2D layered structures. Cadmium(II) bromide formed 1D ladder of 2 and 2D layer of 4, representing an unusual example of Br bond isomerism. Compound 6 has a 1D tape structure with an uncommon 1D inorganic ⋯Cd2(μ3-OH)2–Cd–Cd2(μ3-OH)2⋯ chain. The structural diversity of these materials is reflected in the variety of coordination polyhedra displayed by the cadmium sites: tetrahedral; trigonal bipyramidal; octahedral. The solid state photoluminescence of all compounds have been investigated. However, only compound 6 exhibits photoluminescence with an emission maximum at 435 nm upon excitation at 346 nm. Solid-state density functional theory (DFT) calculations were performed on compound 6. In addition, these compounds were characterized by IR, elemental analysis, and thermogravimetric analysis.

Silver(I) and Lead(II) Halide Compounds with 4-Methyl-1,2,4-triazole-3-thiol

Four novel silver(i) and lead(ii) halide compounds with the 4-methyl-1,2,4-triazole-3-thiol (Hmptrz) ligand, namely [Ag2(mptrz)(μ3-X)]n (X = I (1) and Br (2)) and [Pb4(μ4-O)(mptrz)4(μ2-X)2] (X = I (3) and Cl (4)), have been synthesized and characterized. The structures exhibit different dimensionality depending on the nature of the metal ions. Compounds 1 and 2 are isomorphous and have 2D layered structures based on inorganic [Ag2X2]n infinite chains (X = I and Br), in which the mptrz– ligand displays a novel pentadentate bridging coordination mode. Compounds 3 and 4 have similar structures and are composed of a discrete tetranuclear lead(ii) cluster featuring an oxygen-centred Pb4(µ4-O) tetrahedron. Compounds 1 and 2 display solid-state photoluminescent emission with the maximum at 589 and 420 nm respectively. Compounds 3 and 4 show solid-state photoluminescent emission with the maximum at 710 and 540 nm respectively. Additionally, compounds 1–4 were characterized by IR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis.

Poly[[aqua(μ7-ethylenediaminetetraacetato)dicadmium(II)] monohydrate]

The title compound, {[Cd(2)(C(10)H(12)N(2)O(8))(H(2)O)].H(2)O}(n), consists of two crystallographically independent Cd(II) cations, one ethylenediaminetetraacetate (edta) tetraanion, one coordinated water molecule and one solvent water molecule. The coordination of one of the Cd atoms, Cd1, is composed of five O atoms and two N atoms from two tetraanionic edta ligands in a distorted pentagonal-bipyramidal coordination geometry. The other Cd atom, Cd2, is six-coordinated by five carboxylate O atoms from five edta ligands and one water molecule in a distorted octahedral geometry. Two neighbouring Cd1 atoms are bridged by a pair of carboxylate O atoms to form a centrosymmetric [Cd(2)(edta)(2)](4-) unit located on the inversion centre, which is further extended into a two-dimensional layered structure through Cd2-O bonds. There are hydrogen bonds between the coordinated water molecules and carboxylate O atoms within the layer. The solvent water molecules occupy the space between the layers and interact with the host layers through O-H...O and C-H...O interactions.