Pei-Xiu Yin

Synthesis, Structure, and Luminescent Properties of Hybrid Inorganic-Organic Framework Materials Formed by Lead Aromatic Carboxylates: Inorganic Connectivity Variation from 0D to 3D

The hydro(solvo)thermal reactions of Pb(OAc)(2).3H(2)O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H(3)BTC; 1,4-, 1,2-, and 1,3-H(2)BDC) have yielded a family of inorganic-organic framework materials: [Pb(2)(1,3,5-BTC)(mu(3)-OH)(H(2)O)](n) (Iota), [NaPb(1,3,5-BTC)(H(2)O)](n) (IotaIota), [Pb(1,4-BDC)](n) (IotaIotaIota), [Pb(5)(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb(5)(1,3-BDC)(5)(H(2)O)(2)](2).H(2)O}(n) (V). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis-mass spectrometry, and photoluminescence spectra. They are all three-dimensional structures except for two-dimensional IV. Topology analysis reveals that complexes I an V represent rare (4,8)-connected flu and (3,4)-connected zeolite-like nets, respectively. The five complexes exhibit diverse inorganic connectivity, including a 0D Pb(4)O(16) cluster for I, a 1D Pb-O-Pb chain for II, a 2D Pb-O-Pb network for III and IV, and an unprecedented 3D Pb-O-Pb framework for V. And the diversity in inorganic arrays leads to differences in luminescent properties of these complexes.

Role of molar-ratio, temperature and solvent on the Zn/Cd 1,2,4-triazolate system with novel topological architectures

Five members of the Zn/Cd triazolate family, [Zn(TAZ)(OAc)]n (1), [Zn4(TAZ)6(OAc)2]n (2), [Cd3Cl3(TAZ)3(DMF)2]n (3), [CdCl2(TAZ)]n·n(H2O) (4) and [Cd2Cl(μ4-AmTAZ)2(μ-AmTAZ)]n (5), have been synthesized from TAZ/AmTAZ and corresponding metal salts, where TAZ, AmTAZ and DMF are 1,2,4-triazole, 3-amino-1,2,4-triazole and N,N′-dimethylformamide, respectively. X-ray analysis shows that all compounds except 4 manifest interesting 3D frameworks with novel topologies. Compounds 1 and 2 are temperature-and-solvent controlled assemblies and possess 3D (3,4,6)-connected (3.72)2(32.4.73)(32.4.76.86) topology and 3D (3,6)-connected (4.82)3(83)(46.86.123) topology, respectively. However, compounds 3 and 4 are molar-ratio-dependent compounds. The framework of 3 is a 3D (3,4,5)-connected one with (4.102)(4.62)2(43.62.8)2(64.106) topology, in which the 1D channels are filled with coordinated DMF, while only a 1D chain-like motif is formed in 4. In addition, a 3D (4,6)-connected (3.42.52.6)2(32.42.54.65.72)(32.44.54.64.7) topology is observed in the framework of 5, where AmTAZ is used instead of TAZ in the syntheses of compounds 1–4. Solid state measurements reveal that all these coordination polymers are thermostable and luminescent under ambient conditions.

Protonated 3-amino-1,2,4-triazole templated luminescent lanthanide isophthalates with a rare (3,6)-connected topology

Although 3-amino-1,2,4-triazole (AmTAZ) is often used as a ligand, its templating behavior has never been explored. Presented here are a series of isomorphous lanthanide isophthalates, [Ln(ip)2(H2O)]·(HAmTAZ) (Ln = La (1), Sm (2), Tb (3); ip = isophthalate, AmTAZ = 3-amino-1,2,4-triazole), templated by protonated HAmTAZ+ cations. The three-dimensional (3D) anionic [Ln(ip)2(H2O)]n framework based on rod-like [Ln(COO)4(H2O)]n secondary building units (SBUs) exhibits rare (3,6)-connected (42.6)2(44.62.87.102) topology, and the guest HAmTAZ+ cations are trapped in the channels. Both compounds 2 and 3 show interesting luminescence properties.

Temperature-controlled syntheses of substituted 1,2,4-triazolelead(II) complexes: active lone pair and N-H...X (X = Cl, Br, I) hydrogen bonds.

Three isomorphous lead(II) complexes with a new {N(3)SX}-coordinated (X = Cl, Br, I) mode have been synthesized and characterized by X-ray diffraction. The structural analyses reveal that the coordination environment around the center metal is distinctly influenced by the stereochemical 6s(2) lone pair and N-H...X hydrogen bonds. Additionally, doubly deprotonated trzS(2-) (HtrzSH = 1,2,4-triazole-3-thiol) generated in situ via deamination and dehydrazination of ahtrzS(-) (ahtrzSH = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) was first observed in a semiconducting three-dimensional coordination network at higher reaction temperature.

Novel (3,6)-connected network and (4,6)-connected framework in two copper(II) and cadmium(II) complexes of flexible (2S,3S,4R,5R)-tetrahydrofurantetracarboxylic acid: synthesis, structure, thermostability, and luminescence studies

Two novel coordination polymers, {[Cu2(THFTCA)(phen)] · H2O}n (1) and [Cd2(THFTCA)(H2O)3]n (2) (H4THFTCA = (2S,3S,4R,5R)-tetrahydrofurantetracarboxylic acid, phen = 1,10-phenanthroline), have been prepared under hydro(solvo)thermal conditions and characterized by X-ray diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that both complexes 1 and 2 crystallize in the P21/c space group. The structure of complex 1 is based on 2D (3,6)-connected kgd-type (43)2(46.66.83) layers, which are further extended into a 3D supramolecular architecture through π–π packing interactions of phen. Complex 2 is the first reported Cd-tetrahydrofurantetracarboxylate and represents a complicated 3D metal–organic framework (MOF) structure with (4,6)-connected (44.62)(46.69) topology. The configurations of THFTCA ligands in the two complexes are all meso-(2S,3S,4R,5R) form. The luminescent properties of 2 have also been investigated.

Nanosized lanthanide oxide rods in I1O3 hybrid organic–inorganic frameworks involving in situ ligand synthesis

Presented here are three interesting I1O3 lanthanide-transition metal coordination polymers [Ln2Cu(μ6–O)1/6(μ3–OH)2/3(μ3–OH)2(hpzc)2(H2O)2]·2H2O [Ln = Dy(1), Ho(2), Er(3); Hhpzc = 3-hydroxy-pyrazine-2-carboxylic acid], based on nano-sized Ln-O-Ln inorganic rods and in situ obtained 3-hydroxy-pyrazine-2-carboxylate which came from pyrazine-2,3-dicarboxylic acid (H2pzdc). It is the first time that nanorods are incorporated into metal–organic frameworks.

Capturing in situ generated NHCH–NNH molecule via the templating synthesis of a 4-connected open Cd(II) framework

An unprecedented in situ generated NHCH–NNH molecule successfully templated the formation of a photoluminescent 4-connected open Cd(II) framework with the umc topology, which first demonstrated the ring-opening reaction from the N,S-containing ligand. The results provide a new templating synthetic route to understand the mechanism of hydro(solvo)thermal in situ ligand synthesis via capturing small in situ generated molecular fragments.

Homochiral moganite-type metal–organic framework based on unusual (Ag2Cl)n skeletons

A homochiral hybrid organic/inorganic material {[Ag2(4,4′-bipy)2Cl]·(NO3)}n (1, 4,4′-bipy = 4,4′-bipyridine), with unusual moganite topology, has been constructed by 4,4′-bipy combining argentum halide skeletons, which are formed based on the unprecedented planar μ4-bridging Cl.

CCDC 798304: Experimental Crystal Structure Determination

Related Article: Pei-Xiu Yin, Jian Zhang, Ye-Yan Qin, Jian-Kai Cheng, Zhao-Ji Li, Yuan-Gen Yao|2011|CrystEngComm|13|3536|doi:10.1039/c0ce00762e