Ya-Nan Hou

Synthesis, crystal structure, photoluminescence property and photoelectronic behavior of two uranyl-organic frameworks constructed from 1, 2, 4, 5-benzenetetracarboxylic acid as ligand

By using 1, 2, 4, 5-benzenetetracarboxylic acid as organic ligands, two uranyl coordination complexes, (UO2)2(bta)(DMA)2 (1) and [(UO2)2(bta)(μ3-OH2)]·2[HN(CH3)2]·H2O (2) (H4bta=1, 2, 4, 5-benzenetetracarboxylic acid, DMA=N,N-Dimethylacetamide) were synthesized. The X-ray single crystal analysis revealed that complex 1 exhibits a 3-demensional framework, while complex 2 exhibits a 2-demensional framework. In order to furthermore characterize the two complexes and extend their functional properties, spectroscopies of IR, UV-vis, photoluminescence and surface photovoltage were also studied primarily. In addition, thermogravimetric analyses and photocatalytic studies for complexes 1 and 2 were discussed in detail.

UO22+-amino hybrid materials: structural variation and photocatalysis properties

Four uranyl complexes (UO2)2(μ2-OH)(μ3-OH)(his)(CH3CO2) (his = histidine) (1), [(UO2)2(μ2-OH)(μ3-OH)2(gly)]·1.5H2O (gly = glycine) (2), UO2(CH3CO2)(μ2-OH)(2,2′-bipy) (3) and UO2(CH3CO2)2(2,2′-bipy) (4) were synthesized by the reaction of UO2(CH3CO2)2·2H2O as the metal source, and histidine, glycine and 2,2′-bipy as the ligand in an aqueous system. They were characterized by elemental analysis, IR, UV-vis, single crystal X-ray diffraction analysis and thermal gravimetric analysis. The structural analysis reveals that complex 1 exhibits a one-dimensional chain structure constructed by the building unit [(UO2)4O10(C6O2N3)2], which further extends the chain into 2D supramolecular architectures by hydrogen bonding interactions. For complex 2, uranyl polyhedrons, through edge-sharing, form a 2D wave-like layer and furthermore connect by hydrogen bonding to form a 3D supramolecular structure. Complex 3 is a discrete UO2-2,2′-bipy compound UO2(CH3CO2)(OH)(2,2′-bipy). Complex 4 is also a discrete UO2-acetic-2,2′-bipy compound UO2(CH3CO2)2(2,2′-bipy) which is similar to complex 3. The adjacent molecules were respectively connected by hydrogen bonding to form a 2D supramolecular network for 3 and a 1D supramolecular chain for 4. In order to determine their functional properties, their photoluminescence was characterized and their photocatalytic properties were also studied firstly.

Multi-functional d10 metal–organic materials based on bis-pyrazole/pyridine ligands supported by a 2,6-di(3-pyrazolyl)pyridine with different spanning flexible dicarboxylate ligands: synthesis, structure, photoluminescent and catalytic properties

A series of the novel zinc complexes, Zn3(H2L1)2(ox)3(H2O)2·4H2O (1), Zn(H2L1)(ad)·2H2O (2), Zn2(HL2)2(suc)0.5·(HCOO)·H2O (3), Zn2(HL2)2(glu)·2H2O (4), Zn2(HL2)2 (ad)0.5·(OH)·0.5H2O (5), Zn2(HL2)2(seb)(H2O)·2.5H2O (6), (H2L1 = 2,6-di(5-methyl-1H-pyrazol-3-yl)pyridine, H2L2 = 2,6-di(5-phenyl-1H-pyrazol-3-yl)pyridine, H2ox = oxalic acid, H2ad = adipic acid, H2suc = succinic acid, H2glu = glutaric acid, H2seb = suberic acid) were synthesized hydrothermally from the self-assembly of a Zn(II) ion with different types of the new bi-pyrazolyl pyridine derivative ligands and different spanning flexible dicarboxylic compounds as an auxiliary ligand. They were characterized by elemental analysis, IR and UV–vis spectroscopy, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. We found that they are all molecular compounds using the above detections. The structural analysis indicates that the zinc atom in complex 1 is a six-coordinate mode of ZnO3N3, forming a slightly distorted octahedral geometry, while zinc atoms in complexes 2–6 are all penta-coordination modes of ZnO2N3 and ZnON4 in a distorted bipyramidal geometry. The H2L1 ligand is in the form of a μ1–η1–η1–η1 coordination with metallic Zn in 1 and 2; while the HL2 ligand is in a μ2–η1–η1–η1–η1 coordination mode in 3–6. For the oxalate ligand, there are two kinds of coordination modes, μ2–η1–η1–η1–η1 bridging coordination mode and μ1–η1–η1 terminal coordination mode; the coordination mode of glutaric acid ligand is in the form of μ2–η1–η1; suc2− ligand is in the form of a μ4-bridging coordination fashion with each side carboxylate group in a μ2–η1–η1-monodentate mode; the coordination of the adipic acid ligand presents two coordination modes of μ2–η1–η1and μ4–η2–η2; suberic acid ligand acts in a monodentate terminal coordination mode. In addition, thermal behaviors and photoluminescent properties for 1–6 were all performed and are discussed in detail. The catalytic activity of the complexes is evaluated firstly by the reaction of hydrogen peroxide promoted oxidation of cyclohexane and cyclopentane under mild conditions. It is found that the Zn complexes with five different spanning flexible dicarboxylic acids as an auxiliary ligand with oxalic acid, succinic acid, glutaric acid, adipate acid or sebacic acid, respectively, have potential catalytic activity in the oxidation reaction of cyclohexane.

Synthesis, structures and properties of the catalytic bromination reaction of a series of novel scorperate oxidovanadium complexes with the potential detection of hydrogen peroxide in water.

A series of scorpionate oxovanadium (IV) complexes: [VO(Tp(4I))(pz)(SCN)]·1/2CH2Cl2 (1), [VO(Tp)(pzTp)]·2H2O (2), [VO(Bp)(Tp(4I))] (3) and [VO(C5H7O2)(Tp(4I))]·CH3OH (4) (Bp: [H2B(pz)(2-)], Tp: [HB(pz)(3-)], Tp(4I): [HB(4I-pz)(3-)], pzTp: [B(pz)(4-)]) have been synthesized and characterized by elemental analysis, IR spectra, UV-Vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and thermal gravimetric analysis (TG). Structural analysis shows that the coordination environment of vanadium atom is N5O, to form a distorted octahedron geometry. In addition, the catalytic activities of the bromination reactions for complexes 1 and 2 in phosphate buffer with phenol red as a trap were evaluated primary by UV/Vis spectroscopy, and a practical application of H2O2 detection was firstly observed in the catalytic reaction system.

Synthesis, structure, spectroscopy of four novel supramolecular complexes and cytotoxicity study by application of multiple parallel perfused microbioreactors

Four novel supramolecular complexes [Cd(H2L)2]·(NO3)2·2H2O (1), [Cd(H2L)2]·(OH)2·(EtOH)0.5 (2), [Zn(H2L)(2,6-pdc)]·(2,6-H2pdc)1.5·MeOH·0.5H2O (3) and [Zn(H2L)2][Zn(2,5-Hpdc)3]2·1.5H2O (4) (H2L = 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine, 2,6-H2pdc = 2,6-pyridinedicarboxylic acid, 2,5-H2pdc = 2,5-pyridinedicarboxylic acid) based on pyrazolyl derivatives as ligands were designed and synthesized. They were characterized by elemental analysis, IR and UV-vis spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction. The structural analysis indicates that the central metal atom (cadmium and zinc atoms) is six-coordinated, and possesses a slightly distorted-octahedral configuration. In addition, a cytotoxicity study was performed using multiple parallel perfused microbioreactors and the potential apoptotic effects on adrenal pheochromocytoma cells and human adipose tissue-derived stem cells were examined by flow-cytometric analysis. The results show that the percentage of apoptotic cells becomes gradually higher as the concentration of the supramolecular complex is increased.

Dinuclear vanadium complexes with rigid phenylpolycarboxylate ligands: synthesis, structure, and catalytic bromination reaction with potential detection of hydrogen peroxide

Vanadium complexes (VO)2(2,2′-bipy)2(bta)(H2O)2 (1) and (VO)2(1,10-phen)2(bta)(H2O)2 (2) (H4bta = 1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy = 2,2-bipyridine and 1,10-phen = 1,10-phenanthroline) have been synthesized by the reaction of V2(SO4)3, H4bta, 2,2′-bipy (for 1) and 1,10-phen (for 2) by hydrothermal methods. The complexes were characterized by elemental analysis, IR, UV–vis, thermogravimetric analyses, and single-crystal X-ray diffraction. Structural analyses indicate that 1 and 2 are both VO-bta-N-heterocycle system complexes. The central vanadium is coordinated by N2O4 donors to form a distorted octahedral geometry. The complexes exhibit catalytic bromination activity in a single-pot reaction with conversion of phenol red to bromophenol blue in a mixed solution of H2O-DMF at 30 ± 0.5 °C with pH 5.8, indicating that they can be considered as a functional model of vanadium-dependent haloperoxidases. The practical application of H2O2 detection has also been studied. Graphical Abstract Two oxovanadium complexes, (VO)2(2,2′-bipy)2(bta)(H2O)2 (1) and (VO)2(1,10-phen)2(bta)(H2O)2 (2) (H4bta = 1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy = 2,2-bipyridine and 10-phen = 1,10-phenanthroline), have been synthesized and characterized. The catalytic bromination activity and the practical application of H2O2 detection have been studied.

Synthesis, structures, and catalytic studies of new copper(II) complexes with arene-linked pyrazolyl methane ligands

Two new copper complexes, [Cu2(L1)(dipic)2(H2O)2]⋅2H2O (1) and [Cu2(L2)(dipic)2(H2O)2]⋅3H2O (2) (L1 = 1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 = 1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene; and H2dipic = 2,6-pyridinedicarboxylic acid), were synthesized by the reaction of copper salt, arene-linked pyrazolyl methane ligands, and 2,6-pyridinedicarboxylic acid in 95% C2H5OH. They were characterized by elemental analysis, IR, UV–vis, single-crystal X-ray diffraction analysis, X-ray powder diffraction, and thermogravimetric analysis. We explored the application of the copper complexes in bromination reactions; the complexes exhibited bromination catalytic activity in single-pot reaction for the conversion of phenol red into bromophenol blue. A feasible bromination reaction mechanism of copper complexes was proposed. Graphical abstract Two new copper complexes, [Cu2(L1)(dipic)2(H2O)2]⋅2H2O (1) and [Cu2(L2)(dipic)2(H2O)2]·3H2O (2) (L1 = 1,4-bis((1H-pyrazol-1-yl)methyl)benzene; L2 = 1,4-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)benzene; and H2dipic = 2,6-pyridinedicarboxylic acid), have been synthesized. The application of the copper complexes in bromination reaction was explored, and a mechanism was proposed.

CCDC 854265: Experimental Crystal Structure Determination

Related Article: Xiaoxi Zhang, Na Xing, Fengying Bai, Lijuan Wan, Hui Shan, Yanan Hou, Yongheng Xing, Zhan Shi|2013|CrystEngComm|15|9135|doi:10.1039/C3CE41213J