Zong-Hua Wang

Series of crystalline beryllium phosphates including new templates generated by in situ N-methylation transformation

Four new organically templated beryllium phosphates, [Hmampy][Be(HPO4)2] (1), [dmdabco][Be3(HPO4)4]·(H2O)1.5 (2), [tmpip][Be(HPO4)(H2PO4)]2 (3) and [tmpip][Be2(HPO4)2(H2PO4)]2 (4), where Hmampy = monoprotonated N-methyl-3-(aminomethyl) pyridinium), dmdabco = N,N′-dimethyl-1,4- diazabicyclo[2,2,2]octane and tmpip = N,N,N′,N′-tetramethyl-piperazinium, were hydrothermally synthesized involving in situ generation of structure-directing agents. The Hmampy2+, dmdabco2+ and tmpip2+ templates were in situ generated by methylation of organic cyclic amines: 3-(aminomethyl)pyridine (ampy) in 1, 1,4-diazabicyclo[2,2,2]octane (dabco) in 2, 1,4-dimethyl-piperazine (dmpip) in 3 and piperazine (pip) in 4. This methylation is different from the conventional Eschweiler–Clarke reaction in which an excess of formic acid and formaldehyde is required. Compound 1 contains infinite inorganic chains which are linked by the organic templates in helical hydrogen-bondings, and 2 and 3 possess different layers with eight- and twelve-membered apertures, respectively. Compound 4 has a three-dimensional interrupted open-framework which is constructed from two-dimensional sheets pillared by phosphate nodes, forming intersecting 8-, 10- and 12-ring channels.

Template synthesis and photochromism of a layered zinc diphosphonate

A zinc diphosphonate with protonated 2,4,6-tri(4-pyridyl)-1,3,5-triazine (H3TPT) as the template was hydrothermally prepared. The host layered framework was composed of 1-hydroxyethylidenediphosphonate and zinc ions. The guest H3TPT locates between the adjacent layers, acting as the charge balancer and template. The title compound features rapid photochromism upon irradiation with sunlight or UV light at ambient temperature.

Deoxy-liquefaction of three different species of macroalgae to high-quality liquid oil.

Three species of macroalgae (Ulva lactuca, Laminaria japonica and Gelidium amansii) were converted into liquid oils via deoxy-liquefaction. The elemental analysis, FTIR and GC-MS results showed that the three liquid oils were all mainly composed of aromatics, phenols, alkanes and alkenes, other oxygen-containing compounds, and some nitrogen-containing compounds though there were some differences in terms of their types or contents due to the different constituents in the macroalgae feedstocks. The oxygen content was only 5.15-7.30% and the H/C molar ratio was up to 1.57-1.73. Accordingly, the HHV of the three oils were 42.50, 41.76 and 40.00 MJ/kg, respectively. The results suggested that U. lactuca, L. japonica and G. amansii have potential as biomass feedstock for fuel and chemicals and that deoxy-liquefaction technique may be an effective way to convert macroalgae into high-quality liquid oil.

Ligand-oriented assembly of a porous metal–organic framework by [CuI4I4] clusters and paddle-wheel [CuII2(COO)4(H2O)2] subunits

A novel porous mixed-valence copper–organic framework based on CuI4I4 clusters and paddle-wheel [CuII2(COO)4(H2O)2] moieties was synthesized through a ligand-oriented assembly. The mixed-valence Cu(I)–Cu(II) complex features the coexistence of micro-sized cages and 1D channels and its sorption behaviour has been investigated.

Hydrothermal Synthesis and Structural Characterization of a New Hybrid Zinc Borate, [Zn(dap)2][B4O6(OH)2]

A new zinc borate [Zn(dap)2][B4O6(OH)2] (1, dapxa0=xa01,3-diaminopropane) has been hydrothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallized in the monoclinic P21/c space group, axa0=xa07.0050(4)xa0Å, bxa0=xa07.8160(2)xa0Å, cxa0=xa018.4470(5)xa0Å, βxa0=xa094.571(3)xa0Å, Vxa0=xa01006.78(7)xa0Å3, Zxa0=xa04, R1xa0=xa00.0342, wR2xa0=xa00.0835. Compound 1 displays a novel two-dimensional inorganic–organic hybrid zinc borate layer constructed from the assembly of [B4O6(OH)2]2− clusters, ZnO2N2 tetrahedra and organic dap molecules. The occurrence of infinite Zn–amine–Zn chains in the structure is uncommon and noteworthy in borate materials.

Syntheses and Characterizations of Three Organically Templated Zinc Phosphites with 12-Ring Channels

Three new zinc phosphites, [Hapy]2[Zn3(HPO3)4] (1; apyu2009=u20094-aminopyridine), [H2hepip][Zn3(HPO3)4]·(H2O)0.25 (2; hepipu2009=u2009N-(2-hydroxyethyl)piperazine), and [H2tmdab][Zn3(HPO3)4] (3; tmdabu2009=u2009N,N,N′,N′-tetramethyl-1,3-diaminobutane), have been synthesized and characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single-crystal X-ray diffraction. The frameworks of 1–3 are constructed from 4-connected ZnO4 tetrahedra and 3-connected HPO3 pseudo pyramids with distinct connection mode driven by different organic amine templates. There are 12-membered ring (12-MR) and 8-MR apertures in the (3,4)-connected three-dimensional architecture of 1–3. It is notable that helical chains are observed in the framework of compound 3.