Jian-Gen Huang

Syntheses, structures and investigation of the properties of mercury coordination polymers based on 5-amino-tetrazolate ligands

Four new mercury coordination polymers were successfully synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal analysis, powder X-ray diffraction and single-crystal X-ray diffraction. In these complexes, the chemical valence of mercury is +2, except for complex 1 which is +1. 1 contains [Hg2]2+ metal–metal bonded cores which are bounded by atz− (Hatz = 5-amino-tetrazolate) ligands and features a two-dimensional (2D) uninodal 3-connected ‘hcb’ network. 2 exhibits a trinodal 3D (3,6)-connected ‘apo/alpha-PbO2’ topological net in which 2D [HgCl]nn+ inorganic cation layers are pillared by atz− ligands. In 3, the 2D [HgCl]nn+ cation layers are interconnected by atz− ligands, affording a trinodal 3D (3,6)-connected ‘flu/fluorite’ topological net. 4 is a 3D pillared-layer metal–organic framework based on mixed atz− and isonicotinic ligands, showing a binodal (4,6)-connected ‘fsc’ coordination network. In this work, 1 and 4 were synthesized from an in situ generated tetrazolate ligand, while 2 and 3 were prepared from a commercially available tetrazolate ligand. These results indicate that the final structures of the target complexes will highly depend on the synthetic conditions as well as the preparation methods. Moreover, the photoluminescence properties of these complexes were investigated. Impressively, the non-centrosymmetric complex 3 displays not only a second harmonic generation (SHG) response but also a ferroelectric behavior.

Metal-induced property variation for a series of lanthanide-vanadium porphyrins

Three lanthanide-vanadium porphyrins, [LnV(TPPS)H2O]n (Ln = Tb(1), Dy(2), Er(3); H6TPPS = tetra(4-sulfonatophenyl)porphyrin), have been prepared from hydrothermal reactions and their structures were characterized by single crystal X-ray diffraction technique. The macrocyclic ring of H6TPPS is coplanar and the center is occupied by the vanadium(III) ion. The lanthanide(III) ions are bound by eight oxygen atoms to yield a distorted square anti-prism geometry. They are characteristic of a three-dimensional (3-D) open framework with a void space of around 210 A3. Fluorescence studies reveal that compounds 1–3 exhibit an emission band in the red region with the quantum yields being of 2.0%, 1.4% and 5.0%, respectively. CV/DPV results discover one quasi-reversible wave (1), one reductive peak (2) and two reductive peaks (3). Compounds 1–3 show largely different photophysical and electrochemical properties, although their structures only show tiny difference in lanthanide metal ions. This is due to metal-induced properties variation.

A series of thermal stable lanthanide porphyrins with a condensed three-dimensional porous open framework: Gas adsorption and magnetic properties

A series of lanthanide porphyrins, [LnIII(TPPSIV)]n·nH5O2 (Ln = La, Sm, Eu; H2TPPS = tetra(4-sulfonatophenyl)porphyrin), have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction. These compounds are characterized by a condensed three-dimensional (3-D) porous open framework. Magnetic measurements reveal that these compounds show ferromagnetic, antiferromagnetic and paramagnetic behavior, respectively. All of the compounds exhibit highly thermal stability. The FT-IR and adsorption measurement of CO2 were also studied.

Electrochemistry, photoluminescence and theoretical study of the first 5,10,15,20-tetra-(4-(triazol-1-yl)phenyl) porphyridine complex

The first 5,10,15,20-tetra-(4-(triazol-1-yl)phenyl) porphyridine complex, [Zn2Cl4(5,10,15,20-tetra-(4-(triazol-1-yl)phenyl)porphyridine)]nnCl·nH3O·7nH2O (1) has been synthesized via solvothermal reactions and characterized by single-crystal X-ray diffraction. Complex 1 is characteristic of a one-dimensional (1-D) structure, consisting of neutral [Zn2Cl4(5,10,15,20-tetra-(4-(triazol-1-yl)phenyl) porphyridine)]n chains, isolated chloride ions and lattice water molecules. The zinc ion is in a four-coordinated tetrahedral geometry, and the porphyrin macrocycle is saddle-distorted. Photoluminescence measurement with solid-state samples discovers that it exhibits an emission in the green region of the light spectrum. Time-dependent density functional theory (TDDFT) calculation discovers that this emission can be attributed to the π–π* charge transfer. The cyclic voltammetry (CV) measurement reveals that it possesses an oxidation peak at 0.37 V.

A samarium hybrid with porphyrin and amino acid as mixed ligands: Electrochemical and photophysical properties

A samarium hybrid with porphyrin and amino acid as mixed ligands {[Sm(His)(H2O)][Sm(H3O)3](H2TPPS)2} • 5H2O (1) (His = histidine; H6TPPS = tetra(4-sulfonatophenyl)porphyrin) has been synthesized via a hydrothermal reaction and characterized by single-crystal X-ray diffraction. Compound 1is crystallized in the space group Pi of the triclinic system. Compound 1is characteristic of a three-dimensional (3-D) open framework with the samarium ions in two types of coordinating environments and a saddle-distorted nonplanar porphyrin macrocycle. Compound 1 exhibits fluorescence in the red region. The fluorescence lifetime of 1 is 15.65 ns and the emission quantum yield is 4.1%. The CV/DPV, UV-vis and FT-IR are also reported in detail.