Guo-Ming 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.

An open-framework beryllium phosphite with extra-large 18-ring channels

A novel open-framework beryllium phosphite, [H4tren][Be6(HPO3)8]·(H2O)3 (1, tren = tris(2-aminoethyl)amine), was synthesized under solvothermal conditions. Its structure features a 3D interrupted network with a low density (1.594 g cm−3), and 1 represents the first example of a beryllium phosphite material with extra-large 18-ring channels.

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.

Concise template syntheses of gallium phosphates driven by in situ direct alkylation of aliphatic and aromatic precursors by methanol

A family of open-framework gallium phosphates (GaPOs), namely [dmdabco]0.5[Ga(HPO4)2] (1, dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane), [tmpip]0.5[Ga3(OH)(PO4)3]·(H2O)0.25 (2, tmpip = N,N,N′,N′-tetramethyl-piperazinium), [mpy][Ga3F(PO4)3]·(H2O)0.25 (3, mpy = N-methyl-pyridine), [dmbpy]0.5[Ga2(HPO4)2(PO4)] (4, dmbpy = N,N′-dimethyl-4,4′-bipyridine), and [Hmpip]2[Ga7(OH)(PO4)6(HPO4)2] (5, mpip = N-methylpiperazine) have been fabricated under hydro(solvo)thermal conditions and structurally characterized. The in situ-template-synthesis strategy is firstly used to construct the gallium phosphates. The in situ generated dmdabco2+, tmpip2+, mpy+ and dmbpy2+ templates were derived from the methylation of two distinct types of organic-amine precursors under methanol media: aliphatic 1,4-diazabicyclo[2,2,2]octane (dabco) in 1, 1,4-dimethylpiperazine or 1-methylpiperazine or piperazine (pip) in 2, and aromatic pyridine (py) in 3 and 4,4′-bipyridine (bpy) in 4. Such a unique in situ methylation feature is different from classic Eschweiler–Clarke methylation in which excessive formic acid and formaldehyde is needed. Compound 1 exhibits infinite inorganic chains connected by hydrogen bonds to generate a 3D supramolecular framework; compounds 2 and 3 are isomorphous and constructed from a Ga6P6 secondary building unit (SBUs), forming a 3D pcu architecture with intersecting 8-membered channels; compound 4 possesses an inorganic layered structure and compound 5 features an interesting 3D open-framework architecture with helical channels.

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.

Cyclohexane-1,4-diammonium tetrahydroxotetraborate 2.5-hydrate

In the title compound, [C6H10(NH3)(2)](2+) center dot[B4O5(OH)(4)](2-) center dot 2.5H(2)O, the asymmetric unit contains one anion, two half-cations and 2.5 water molecules. Each cation is centrosymmetric. In the crystal structure, the anions are connected to each other via hydrogen bonding, forming a three-dimensional framework with rectangular channels, which are occupied by the templating organic amine cations and guest water molecules.

Poly[bis(μ4-benzene-1,2-dicarboxylato)di-μ3-isonicotinato-dilanthanum(III)]

In the title compound, [La(2)(C(8)H(4)O(4))(2)(C(6)H(4)NO(2))(2)](n), there are two crystallographically independent La centres, both nine-coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxylate groups of isonicotinate (IN(-)) and benzene-1,2-dicarboxylate (BDC(2-)) ligands to form La-carboxylate chains, which are further expanded into a three-dimensional framework with nanometre-sized channels by La-N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta- and heptadentate chelating-bridging modes, respectively.

An inorganic–organic hybrid framework from the assembly of an electron-rich diphosphonate and electron-deficient tripyridyl moiety

The combination of an electron-rich zinc diphosphonate layer and electron-deficient 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) generates a 3D inorganic–organic hybrid with an [–ED–EA–ED–EA–] arrangement (ED = electron donor and EA = electron acceptor), which exhibits a wide and rapid photoresponse upon exposure to the stimulus of sunlight, UV light and X-rays at ambient temperature. Notably, the coloration time is 0.1 s when exposed to UV light (320 nm) generated from a Xe-lamp (150 W).

Inorganic–organic hybrid zinc phosphites with fluorescence/phosphorescence dual emission performances

An innovative and feasible strategy has been explored to prepare stable and highly effective room temperature fluorescence/phosphorescence dual emission materials, in which N-containing organic aromatic structure-directing agents were coordinated to metal phosphite frameworks.