Triazoles and tetrazoles: Prime ligands to generate remarkable coordination materials

A series of Pb(II) coordination polymers [Pb(ndc)(dpp)] (1), [Pb(ndc)(ptcp)].0.5 H2O (2), [Pb(ndc)(dppz)] (3), [Pb(ndc)(tcpn)(2)] (4), [Pb2(ndc)2(tcpp)] (5), [Pb(Hndc)2].H2O (6), [Pb(ndc)(dma)] (7), [Pb(bdc)(dma)] (8), [Pb(trans-chdc)(H2O)] (9), and [Pb2(cis-chdc)2].NH(CH3)2 (10), where ndc=1,4-naphthalenedicarboxylate, dpp=4,7-diphenyl-1,10-phenanthroline, ptcp=2-phenyl-1H-1,3,7,8-tetraazacyclopenta[l]phenanthrene, dppz=dipyrido[3,2-a:2',3'-c]phenazine, tcpn=2-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)naphthol, tcpp=4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol, dma=N,N-dimethylacetamide, bdc=1,4-benzenedicarboxylate, and chdc=1,4-cyclohexanedicarboxylate, have been synthesized from a hydrothermal or solvothermal reaction system by varying the ligands or the solvents. Compounds 1-5 crystallize with an N-donor chelating ligand and an aromatic dicarboxylate linker. Compounds 1-4 are 1D polymers with different pi-pi stacking interactions, whereas compound 5 consists of 2D layers. The structures of compounds 7, 8, and 10 are 3D frameworks formed by connection of the Pb(II) centers by organic acid ligands. Compound 7 is chiral although the ndc ligand is achiral, while the framework of 8 is a typical 3D (3,4)-connected net. Compound 10 is the first example of Pb(II) wheel cluster [Pb(8)O(8)] units bridged by carboxylate groups. Compound 6 contains 1D chains which are further extended to a 3D structure by pi-pi interactions. Compound 9 consists of a 2D network constructed by Pb(II) centers and trans-chdc ligands. The structural differences between 7 and 8 and between 9 and 10 indicate the importance of solvents for framework formation of the coordination polymers. By varying the solvent the cis and trans conformations of H(2)chdc in 9 and 10 were separated completely. The photoluminescence and nonlinear optical properties of the coordination polymers have also been investigated.

Structural variation from 1D to 3D: effects of ligands and solvents on the construction of lead(II)-organic coordination polymers.

Four novel highly connected metal–organic frameworks (MOFs) based on d10 metals and triangular ligands, namely, [Ag7(4,4′-tmbpt)(HL)2(L)(H2O)] (1), [NaCd3(4,4′-tmbpt)(L)2(OH)]·H2O (2), [Cd3(3,3′-tmbpt)2(L)2(H2O)2]·3.5H2O (3), and [Cd3(3,4′-tmbpt)2(L)2(H2O)]·1.5H2O (4) (H3L = 5-(4-carboxybenzyloxy)isophthalic acid, 4,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole, 3,3′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole, and 3,4′-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole) have been synthesized under hydrothermal conditions. Compound 1 features a three-dimensional (3D) (3,12)-connected net based on heptanuclear [Ag7(COO)7] units. Compound 2 displays a 3D (3,4,10)-connected net constructed by tetranuclear [NaCd3(μ3-OH)(COO)5]+ units. Compound 3 exhibits a 3D (3,4,8)-connected net based on binuclear [Cd2(COO)2] units. Compound 4 is a 3D binodal (3,9)-connected framework constructed by trinuclear [Cd3(COO)4] unit...

A Series of Highly Connected Metal–Organic Frameworks Based on Triangular Ligands and d10 Metals: Syntheses, Structures, Photoluminescence, and Photocatalysis

A Multifunctional Metal–Organic Open Framework with a bcu Topology Constructed from Undecanuclear Clusters

Two polyoxometalate-templated organic–inorganic hybrid porous frameworks, namely, [Cu2(H2O)2(bpp)2Cl][PM12O40]·∼20H2O (for 1, M = W; for 2, M = Mo; bpp = 1,3-bis(4-pyridyl)propane), were self-assembly obtained and structurally determined by elemental analyses, inductively coupled plasma analyses, infrared spectroscopy, and single-crystal X-ray diffraction analyses. Single-crystal X-ray analysis of these crystals revealed that both of the structures are constructed from eight-connected three-dimensional coordination polymer hosts [Cu2(H2O)2(bpp)2Cl]n3n+ and ball-shaped Keggin-type guests [PM12O40]n3n− as templates. The polymer hosts resulted from a bcc-type framework with nanotubes, and the nanotubes can be regarded as a tetra-stranded helix structure. Furthermore, compounds 1 and 2 exhibit photoluminescent properties at ambient temperature, and the compound 2 bulk-modified carbon paste electrode (2-CPE) displays good electrocatalytic activity toward the reduction of nitrite.

Self-assembly of organic-inorganic hybrid materials constructed from eight-connected coordination polymer hosts with nanotube channels and polyoxometalate guests as templates.

Lee Gin Lin

Papers

Crystal Engineering: Toward Intersecting Channels from a Neutral Network with a bcu‐Type Topology