Multifunctional homochiral lanthanide camphorates with mixed achiral terephthalate ligands.

Seven homochiral lanthanide camphorates with mixed achiral terephthalate ligands, namely, {Ln(2)(cam)(2)(bdc)(H(2)O)(2)}·DMF [Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7); d-H(2)cam = d-(+)-camphoric acid; H(2)bdc = 1,4-benzenedicarboxylic acid; DMF = N,N'-dimethylformamide], have been solvothermally synthesized. Single-crystal X-ray diffraction analyses reveal that compounds 1-7 are isostructural and crystallize in orthorhombic, chiral space group P2(1)2(1)2(1). These structures feature three-dimensional open frameworks based on rodlike [Ln(2)(OCO)(6)(H(2)O)(2)](n) secondary building units, with the guest DMF molecules occupying the void space of the host {Ln(2)(cam)(3)(bdc)(H(2)O)(2)} framework. The photophysical and magnetic properties of some of these complexes have been investigated. Notably, the terbium compound 4 is highly emissive with a quantum yield of 63.68%. Additionally, thermogravimetric analyses, variable-temperature IR spectroscopy, and powder X-ray diffraction of 2 as a representative were performed to determine its thermal stability, which indicates that the framework still remains intact until 300 °C.

Ag(I)-mediated in situ dehydrogenative coupling of 3-amino-1,2,4-triazole into 3,3'-azobis(1,2,4-triazole) in Cd(II) coordination polymers.

Ag(I)-mediated in situ generation of 3,3'-azobis(1,2,4-triazole) (AzTAZ) from 3-amino-1,2,4-triazole (AmTAZ) through dehydrogenative coupling has been realized during the crystallization process of two Cd(II) coordination polymers with novel topological architectures: a (3, 4, 5)-connected (4 x 6(2))(2)(4 x 6(7) x 8(2))(2)(6(5) x 10) net for [Cd(2)(AmTAZ)(2)(AzTAZ)](n) (1) and a 4-connected (6(2) x 8(4))(6(4) x 8(2))(6(5) x 8)(2) net for [Cd(AzTAZ)(2)(H(2)O)](n) (2), whereas AmTAZ retains its original form in a heterometallic complex, [Ag(2)Cd(AmTAZ)(4)](n) (3).

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.

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.

New coordination motifs of melamine directed by N-H---X (X = Cl or Br) hydrogen bonds.

Unusual mu(2)- and mu(3)-coordination modes of melamine are found in two organic-inorganic hybrid copper halides, [Cu(2)Br(2)(MA)](n) (1) and [Cu(3)Cl(3)(MA)](n) (2) (MA = melamine), in which the MA ligand affords two N-heterocycle N atoms to link (Cu(2)Br(2))infinity stairs and serves as a novel mu(3) bridge to give a 3D framework, respectively.