Jian Tong

Two chiral Zn(II) metal–organic frameworks with dinuclear Zn2(COO)3 secondary building units: a 2-D (6,3) net and a 3-D 3-fold interpenetrating (3,5)-connected network

The reaction of Zn(II) and 4,4′,4′′-(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))-tribenzoic acid (H3BBC) without or with the presence of 2-amino-1,4-benzenedicarboxylic acid (NH2-H2BDC) under solvothermal conditions leads to the generation of two novel Zn(II) coordination polymers, [Zn(BBC)(H2O)2](Me2NH2)·12DMF (1) and [Zn2(BBC)(NH2–BDC)](Me2NH2)·10DMF (2), which feature a 2D (6,3) net and a 3D three-fold interpenetrating (3,5)-connected network, respectively. The resulting crystals of 2 were not a racemic mixture but enantiomeric excess, which was confirmed by the measurement of optical rotation of bulk samples using the solid circular dichroism (CD) spectra based on large crystals from one crystallization. Two compounds exhibit strong photoluminescence in the solid state at room temperature.

Crystal engineering of a hybrid metal–organic host framework and its single-crystal-to-single-crystal guest exchange using second sphere coordination

By means of crystal engineering principles, a new second sphere coordination adduct has been synthesized using charge-assisted hydrogen bonds and self-assembling [CdBr6]4−and Br− anions with a V-shaped diprotonated cation. The second sphere adduct is homologous to a copper network, forms a host framework with 1D channels and has good thermal stability (200 °C) upon guest release. The [CdBr6]4− anion shows Jahn–Teller distortion as revealed by X-ray crystallography. Guest exchange via a single-crystal-to-single-crystal manner is reported. The guest behavior is different to that of the homologous Cu adduct due to the pore size effect.

Co-crystal of [CuCl4]2− and L1 and its inclusion compounds with three different guests (L1 = N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine)

In this paper, we have built up the organic-inorganic hybrid co-crystal (1) by using the derivative of ethylenediammonium cations (N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine, L1) and [CuCl4]2− anions. The reaction was carried out by mixing MeOH solution of CuCl2·2H2O and HCl/MeOH solution of L1 at room temperature. Two types of inclusion compounds can be formed when using different guest molecules. When guest molecules, such as anthracene or phenanthrene, were included, it resulted in the formation of interlayered structures: anthracene ⊂ [H2L1]2+·[CuCl4]2− (2) and phenanthrene ⊂ [H2L1]2+·[CuCl4]2− (3). When β-naphthyl phenol were included, it led to the formation of pillared-layered complexes of [1-chloride-β-naphthyl phenol]1.0·[β-naphthyl phenol]0.5·[methanol]1.0 ⊂ 2[H2L1]2+·2Cl−·[CuCl4]2− (4).

Theoretical and experimental determination of the number of water molecules breaking the structure of a glycine-based ionic liquid

The effects of water on the structures of the amino acid ionic liquid (IL) 1-ethyl-3-methylimidazolium glycine ([emim][Gly]) are explored by a classical simulation method. The density and surface tension of the [emim][Gly]–H2O mixture are experimentally studied by a standard addition method. Simulation and experiment show that the density of the [emim][Gly]–H2O mixture reaches the maximum at 2–4 mass% water. Different analysis tools, including radial distribution, an interstice model, and molecular intrinsic characteristic contours are used to describe the structural modifications of the [emim][Gly] and ionic aggregates as a function of the solution concentration. At xw < 0.33 (mole fraction), the isolated water and dimer are located at the interstices formed between the ions, do not modify the network of ILs, and slightly strengthen the interactions between the cation and anion. Consequently, a turnover in the evolution of the IL structures and properties ensues. At 0.33 < xw < 0.50, the formation of relatively large water clusters, such as trimers and tetramers, leads to interstice distention, breakage of the cation–anion network, and gradual loosening of the interactions. With a further increased water concentration, a bicontinuous phase is generated and ionic clusters disperse in a continuous water phase. The size and morphology of the water aggregates are evaluated and analyzed by several statistical functions.

Significant enhancement of visible light photocatalytic activity of the hybrid B12-PIL/rGO in the presence of Ru(bpy)32+ for DDT dehalogenation

A new B12-PIL/rGO hybrid was prepared successfully through immobilizing a B12 derivative on the surface of poly(ionic liquid) (PIL)-modified reduced graphene oxide (rGO) by electrostatic attraction and π–π stacking attraction among the different components. The hybrid catalyst showed an enhanced photocatalytic activity in the presence of Ru(bpy)32+ for 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) dechlorination with ∼100% conversion. Especially, the yield of didechlorinated products could reach 78% after 1 h of visible light irradiation, which should be attributed to a synergistic effect of B12, rGO and PIL in B12-PIL/rGO, including their respective catalytic performance, the excellent electron transport of rGO and the concentration of DDT and 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD) on the surface of B12-PIL/rGO. Furthermore, the hybrid catalyst was easily recycled for use without obvious loss of catalytic activity.

Structure and inclusion behaviour of five supramolecular inclusion solids constructed from flexible organic layers with [Fe(CN)6]3– as pillars by second-sphere coordination

In the paper, a series of new pillar-layered supramolecular complexes have been built up through second-sphere coordination. Three N,N,N′,N′-tetrabenzyl diamine ligands [N,N,N′,N′-tetrabenzyl-ethylenediamine (L1), N,N,N′,N′-tetrabenzyl-2-butyne-1,4-diamine (L2) and N,N,N′,N′-tetrabenzyl-(p-xylylene)-diamine (L3)] were synthesised, and can react with [Fe(CN)6]3 via second-sphere coordination, yielding pillar-layered supramolecular complexes, [H2L1]0.5·[Fe(CN)6]0.5 ⊃ 0.5H3O·1.5H2O (Crystal 1), [H2L2]0.25·[Fe(CN)6]0.25 ⊃ 0.5H3O·0.5H2O (Crystal 2) and [H2L3]·[Fe(CN)6] ⊃ Cl·ethylene glycol·H2O (Crystal 3). The 3D networks are organic layers formed by the self-assembly of the ligands through extensive hydrogen-bonding interactions (π…π stacking or C–H…π interactions) and further interconnected by [Fe(CN)6]3 − in a pillar fashion, constructing into pillar-layered networks with channels accessible to various guest molecules. The inclusion property of [H2L1]·[Fe(CN)6] was studied; varieties of guest molecules, such as ethanol and tetrahydrofuran, can be included in the framework and lead to the formation of different inclusion complexes [H2L1]·[Fe(CN)6] ⊃ (guest) n (crystal 1, 4–5).

Polymorphism and photoluminescence in a naphthalene-based ligand, and its supramolecular structures through second-sphere coordination with the [CoCl4]2− anion

A naphthalene-based ligand, N,N,N′,N′-tetrabenzyl-naphthalene-1,5-diamine (L1) has been synthesized and crystallized as two polymorphs, α and β. There are no strong hydrogen bonding donors, instead C–H⋯π interactions play critical roles in the stabilization of the structures of the two polymorphs with different packing motifs. The ligand L1 can be doubly protonated and coordinate with the “second-sphere” of [CoCl4]2− using N–H hydrogen bond donors to form two neutral supramolecular complexes [H2L1]2+[CoCl4]2− (1) and EtOH ⊂ [H2L1]2+[CoCl4]2− (2). L1 in 1 and 2 adopts the arrangement manner of stable polymorph α. The [CoCl4]2− anions are connected with L1 through N–H⋯Cl interactions, meanwhile, the anion [CoCl4]2− acting as an “off–on” switching template controls the photoluminescence.

Synthesis, characterization, and crystal structure of cobalt(II) and zinc(II) complexes with a bulky Schiff base derived from rimantadine

Two novel complexes, C38H48CoN2O2 (I) and C38H48N2O2Zn (II), were prepared through an analogous procedure with a corresponding metal chloride and a bulky Schiff base ligand (HL) which derived from rimantadine and salicylaldehyde in appropriate solvents, respectively. They were structurally characterized by the means of IR, UV-Vis, elemental analysis, molar conductance, PXRD and single-crystal X-ray diffraction (CIF files nos. 946735 (I), 893304 (II)). Single-crystal X-ray diffraction analysis reveals that I belongs to the triclinic system,

Significant photoelectric conversion properties of multilayer films formed by a cationic zinc phthalocyanine complex and graphene oxide

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