Jinli Zhu

A new Co-nitroimidazolate–dicarboxylate pillared-layer network with various types of channels and ultra-large cages for gas uptake

A novel porous coordination polymer based on a Co-nitroimidazolate–dicarboxylate pillared-layer network, namely, [Co7(bdc)6(nIm)2(H2O)6]·3H2O·3DMF, (1, H2bdc = 1,4-benzenedicarboxylic acid, nIm = 2-nitroimidazole), has been synthesized by a solvothermal reaction. The microporous layers of 1 consisted of two kinds of SBUs, six-connected Co3(O2CR)6 and three-connected [Co2(O2CR)3]+, forming unprecedented Co3-Co2-bdc-based layers with three types of diamonded grids in the bc plane. The layers are further linked by bidentate-bridging nIm ligands as pillars into a 3-D metal–organic framework with two kinds of rectangular channels parallel to the c axis. It is worth mentioning that compound 1 also exhibits uniquely polyhedral cages with a maximum diagonal dimension of up to 31.019 A, which has fallen in the scope of mesoporous (2–50 nm). To systematically evaluate the channels and special cages, the adsorption ability of 1 was measured by N2, H2 and CO2 sorption experiments. Topological analysis indicates that compound 1 adopts a new topological structure with a point symbol of {412·614·82}{46}2. Moreover, thermal gravimetric analysis (TGA) of as-synthesized 1 reveals a stability range up to 311 °C.

Synthesis, structures, and luminescence of two 2-D microporous metal-organic frameworks in the zinc (cadmium)-dicarboxylate-imidazolate system

Abstract Two 2-D microporous metal–organic frameworks, [Zn(BDC)(MbIm)]·2DMF (1) and [Cd3(BDC)3(MbIm)2(DMF)2]·2DMF (2), have been synthesized by solvothermal reaction of 1,4-benzenecarboxylic acid (H2BDC) and 2-methylbenzimidazole (MbIm) with zinc/cadmium nitrate. Single-crystal X-ray diffraction analysis indicates that 1 consists of the well-known zinc paddle-wheel motif which is linked by bridging dicarboxylates to form 2-D square grids. The 2-D layers stack offset due to the effect of the spatial structure of MbIm ligand and hydrogen-bonding interaction between MbIm and guest molecules. Similarly, 2 is constructed by six-connected Cd3(μ-O2CR)6(MbIm)2 units and bridging carboxylates, resulting in a 2-D layer structure with triangular grids. Topology analysis reveals that 1 exhibits a 2-D tetragonal plane network with {44·62} topology symbol, while 2 possesses a six-connected {36·46·53} topological network. Analysis of the luminescence spectra demonstrates that the complexes have good luminescent intensities with greater red-shift (82 nm for 1 and 69 nm for 2) corresponding to free MbIm. Elemental analyses, infrared spectra, powder X-ray diffraction, and thermogravimetric analyses of 1 and 2 have been investigated.

Green, Rapid, and Universal Preparation Approach of Graphene Quantum Dots under Ultraviolet Irradiation

It is of great significance and importance to explore a mild, clean, and highly efficient universal approach for the synthesis of graphene quantum dots. Herein, we introduced a new green, rapid, and universal preparation approach for graphene quantum dots via the free-radical polymerization of oxygen-containing aromatic compounds under ultraviolet irradiation. This approach had a high yield (86%), and the byproducts are only H2O and CO2. The obtained graphene quantum dots were well-crystallized and showed remarkable optical and biological properties. The colorful, different-sized graphene quantum dots can be used in fluorescent bioimaging in vitro and in vivo. This approach is suitable not only for the preparation of graphene quantum dots but also for heteroatom-doped graphene quantum dots.

A novel glycopolymeric ultraviolet absorber covering UV-A and UV-B ranges

In this communication, a novel biocompatible polymeric ultraviolet absorber (UVA), poly(HAB-co-OAG-co-AMC) (PHOA), covering UV-A and UV-B ranges was designed and prepared. The photo-antioxidant tests indicate that there is a synergism between UV-A and UV-B monomers. The cytotoxic experiments demonstrate that PHOA has good biocompatibility.

Penta­carbonyl-1κ2C,2κ3C-(ferrocenyl­diphenyl­phosphine-1κP)[μ-2-(4-methyl­phen­yl)-2-aza­propane-1,3-dithiol­ato-1:2κ4S,S′:S,S′]diiron(I)(Fe—Fe)

The title compound, [Fe2(C9H11NS2){Fe(C5H5)(C17H14P)}(CO)5], was prepared as an azadithiolato–iron model for the iron-only hydrogenase active site. The Fe2S2 unit exhibits a butterfly conformation and the ferrocenyldiphenylphosphine ligand is trans to the Fe—Fe bond. The Fe—Fe distance of 2.5160 (8) Å is longer than found in related model structures. Intramolecular C—H⋯S and intermolecular C—H⋯O hydrogen bonds are observed.

Rational design and synthesis of an amino-functionalized hydrogen-bonded network with an ACO zeolite-like topology for gas storage

Based upon the typically hydrogen-bonded network, metal–organic cubes, the amino functional group was first introduced onto the surface of the cube to raise the polarizability of the framework by in situ hydrolysis of the precursor 2-amino-4,5-dicyanoimidazole (ADCIm) with octahedral In3+ ions under solvothermal conditions, resulting in a supramolecular network with very high CO2 (135.8 cm3 g−1 at 273 K/1 atm) and H2 (2.03 wt% at 77 K/1 atm) adsorption capacities and an exceptional thermostability range up to 416 °C.

Synthesis and characterization of a novel polymeric ultraviolet absorber and its properties

A novel polymeric ultraviolet absorber (UVA) poly (HAB-co-AMC-co-AA) (PHHA) has been prepared by solution copolymerization from 2-hydroxy-4-acryloy benzophenone (HAB), p-acryloy-methyl cinnamate (AMC) and acrylic acid and analyzed using FT-IR, UV–Vis, 1H NMR and GPC. The results revealed two PHHA absorption peaks in UV-A and UV-B. Polymerizable monomer HAB was synthesized by the reaction of 2,4-dihydroxybenzophenone (UV-0) and acryloyl chloride (AC). Another monomer, AMC, was prepared from p-hydroxy-methyl cinnamate and AC. The results showed that HAB and AMC have high UV-absorbing performance in UV-A and UV-B, respectively. The photoantioxidant ability tests indicated that PHHA is an effective polymeric UVA that covers UV-A and UV-B ranges, and a synergism between the two monomers was observed.

Crystal structure of poly[bis­(μ-2-amino-4,5-di­cyano­imidazolato-κ2N1:N3)-trans-bis­(N,N′-di­methyl­formamide-κO)cadmium]

The title compound, [Cd(C5H2N5)2(C3H7NO)2]n, is a two-dimensional coordination polymer extending parallel to (100). Notably, both the primary amino group and the cyano groups are involved in hydrogen-bonding interactions with DMF ligands to direct the assembly and stabilize the crystal packing.

Crystal structure of aqua­bis­[4-(methyl­sulfan­yl)benzoato-κO](1,10-phenanthroline-κ2N,N′)copper(II) monohydrate

In a hydrated CuII complex with 1,10-phenanthroline and 4-(methylsulfanyl)benzoate ligands, a three-dimensional supramolecular network is formed through weak intermolecular C—H⋯O and C—H⋯S interactions and π-stacking between the planes of phenanthroline and the aromatic rings of symmetry-related 4-(methylsulfanyl)benzoate ligands.

Penta­carbonyl-1κ2 C,2κ3 C-(4-iodo­phenyl isocyanide-1κC)(μ-propane-1,3-dithiol­ato-1:2κ4 S,S′:S,S′)iron(I)(Fe—Fe)

In the title compound, [Fe2(C7H4IN)(C3H6S2)(CO)5], the Fe—Fe distance of 2.5156 (11) Å compares well with that in related model structures. The phenyl isocyanide ligand is in the basal position and trans to the S atoms of the propanedithiolate ligand due to steric hindrance. The crystal structure features C—H⋯O interactions.