基于分子催化剂光驱动水氧化器件的研究进展

光解水制氢是人们解决未来能源危机的一种重要构想,构建高效的光电化学池是实现这一构想的重要途径,而光驱动水氧化的顺利进行是实现这一过程的关键.本文总结了近年来基于分子催化剂及染料敏化的光驱动水氧化分子器件的研究和进展,介绍了这些分子器件的组装和性能研究等,并根据这些研究的优点和不足提出一些浅见.     

Study on ligation of copper complexes of the quinolone antibacterial drugs and octamolybdates POMs

By introducing different quinolone antibacterial drugs into the octamolybdates POMs, four new compounds, [Cu^II(L¹)₂(H₂O)₂]H₂[β-Mo₈O₂₆]·4H₂O (1), [Cu^II₂(L²)₄][δ-Mo₈O₂₆]·4H₂O (2), [Cu^II₂(L³)₂(H₂O)₂][β-Mo₈O₂₆] (3), [Cu^II₂(L⁴)₂(H₂O)₄][β-Mo₈O₂₆]·2H₂O (4) (where L¹ = Enrofloxacin; L² = Pipemidic Acid; L³ = Norfloxacin; L⁴ = Enoxacin), have been synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, isolated Cu-Enrofloxacin coordination subunits array the both sides of β-Mo₈O₂₆, forming 3D supramolecular structure via noncovalent interactions. And the Cu-Pipemidic Acid subunits covalently link δ-Mo₈O₂₆ to form 3D supramolecular structures via short interactions in 2. In 3, the Cu-Norfloxacin motif exhibits 1D chain structure, and the tetra-dentate β-[Mo₈O₂₆]⁴⁻ clusters interact with neighboring chains to construct a 2D sheet. Similar to that of 3, the Cu-Enoxacin subunit in 4 exhibits 1D chain structure, and the bi-dentate β-[Mo₈O₂₆]⁴⁻ clusters interact with neighboring chains to construct a 2D sheet. Due to the introduction of different drug molecules, the octamolybdates POMs exhibit different isomers and structures, which bring different properties. The antitumor activities of compounds 1-4 in vitro were studied by MTT experiments, and the results show that introduction of different drug molecules onto the polyoxoanion surface can affect their antitumor activities.     

Synthesis and Structural Characterization of Three Novel Macrocyclic Coordination Complexes Formed by Self-assembly of Bridged Bi-or Tetrapyridine with Transition Metal Salts

Serf-assembly of a ferrocenyl-bridged bipyridine ligand bpef [bpef=1, 1＇-bis（trans-2-pyrid-4＇-ylethenyl）ferrocene] with silver triflate in CH2Cl2/MeOH or mercuric diiodide in MeCN/CH2Cl2 gave the corresponding macrocyclic coordination complexes [bpef]2[AgSO3CF3]2 （1） and [bpef]2[Hg3I6] （2） in 93% and 89% yields, respectively, whereas the pentaerythritolyl-bridged tetrapyridine ligand ptpc [ptpc=pentaerythritol tetrakis-（4-pyridinecarboxylate）] reacted with cobalt thiocyanate via self-assembly to afford the macrocyclic coordination polymer [Co（NCS）2（ptpc）], （3） in 90% yield. The X-ray diffraction analyses for 1-3 confirmed their novel macrocyclic structures and revealed that （i） the two silver atoms in complex 1 have an essentially linear geometry with N-Ag-N bond angle of 175.7° and 172.9°, （ii） the geometry of the middle mercury atom in complex 2 is square-planar, while the other two mercury atoms in the other two complexes are tetrahedral, and （iii） all the cobalt atoms in complex 3 adopt an octahedral geometry. In addition, the synthetic procedure for the known tetrapyridine ligand ptpc has been improved.     

球形大孔树脂担载PEI对CO2的吸脱附行为

以球形大孔树脂（SMR）、聚乙二醇分别作聚乙烯亚胺（PEI）的载体和黏结剂,制得PEI／SMR吸附材料．考察了PEI／SMR材料对CO2的吸脱附性能,并对吸附过程进行了分析．研究结果表明：（1）当PEI担载量为40％、吸附温度为30℃时,PEI／SMR样品对C02的平衡吸附量达4．02mrnol／g,并具有良好的吸脱附循环性能;（2）当模拟烟道气中的湿度为14．5％时,由于部分H20参与了化学反应,使得PEI／SMR样品对C02的平衡吸附量提高了5．7％;（3）C02在PEI／SMR的吸附,先是CO2分子吸附在SMR材料的表面,然后被吸附的CO2分子从表面扩散进入PEI主体相进行化学反应．     

Photochemical hydrogen production with molecular devices comprising a zinc porphyrin and a cobaloxime catalyst

Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)phenyl]10,15,20-triphenylporphyrin),for light-driven hydrogen generation were prepared and spectroscopically characterized.The zinc porphyrin photosensitizer and the Co III-based catalyst unit are linked by axial coordination of a pyridyl group in the periphery of zinc-porphyrin to the cobalt centre of catalyst with different lengths of bridges.The apparent fluorescence quenching and lifetime decays of 1 and 2 were observed in comparison with their reference chromophores,Zn(PyTPP)(3) and Zn(apPyTPP)(4),suggesting a possibility for an intramolecular electron transfer from the singlet excited state of zinc porphyrin unit to the cobalt centre in the molecular devices.Photochemical H2-evolving studies show that complexes 1 and 2 are efficient molecular photocatalysts for visible light-driven H2 generation from water with triethylamine as a sacrificial electron donor in THF/H2 O,with turnover numbers up to 46 and 35 for 1 and 2,respectively.In contrast to these molecular devices,the multicomponent catalyst of zinc porphyrin and [Co(dmgH) 2 PyCl] did not show any fluorescence quenching and as a consequence,no H2 gas was detected by GC analysis in the presence of triethylamine with irradiation of visible light.The plausible mechanism for the photochemical H2 generation with these molecular devices is discussed.     

Study of the interaction of Azur B with DNA and the determination of DNA based on resonance light scattering measurements

Based on the measurements of molecular absorption and resonance light scattering (RLS), the aggregation of Azur B (AB) was in a medium of pH ranging from 1.98 to 2.56 and ionic strength <0.12 M. The presence of double stranded DNA prompts the aggregation, resulting in enhanced RLS signals. Linear relationships were achieved between the enhanced RLS intensity at 359.7 nm and DNA concentration in the range of 0-4.5 μg ml⁻¹ for both calf thymus DNA (ctDNA) and fish sperm DNA (fsDNA) if 3.0×10⁻⁵ M AB was employed. The 3σ limits of detection were 9.3 and 8.9 ng ml⁻¹ for ctDNA and fsDNA, respectively. Five synthetic samples were analysed satisfactorily.     

Electrochemical water oxidation by photo-deposited cobalt-based catalyst on a nano-structured TiO2 electrode

A cobalt-based catalyst was directly photo-deposited on the surface of a widely used n-type nano-structured semiconductor(TiO 2).Different thicknesses of the TiO 2 films as well as different time of photo-deposition of the Co-based catalyst on TiO 2 films have been optimized.It was found that the electrode with 3 layers of TiO 2 film(in 8 m thickness) and 1 hour photo-deposition of the cobalt-based catalyst by light irradiation from a 500 W Xenon lamp gave the highest current density(～5 mA/cm 2).Using this cobalt-modified TiO 2 film as a working electrode in an electrochemical device,highly efficient water oxidation has been demonstrated in a pH 7.0 aqueous solution with low overpotential.     

Recent studies on chemistry of novel μ-CO-containing butterfly Fe/E (E=S,Se,Te) cluster salts

This article describes recent developments in chemical study on a series of butterfly-shaped μ-CO-containing Fe/E (E = S, Se, Te) cluster salts. These salts include eleven novel cluster anions, which are the single butterfly one μ-CO-containing [(μ-RE)(μ-CO)Fe2(CO)6]- (A), the double butterfly two μ-CO-containing {[(μ-CO)Fe2(CO)6]2(μ-EZE-μ)}2- (B, E = S; C, E = Se), the triple butterfly three μ-CO- containing {[(μ-CO)Fe2(CO)6]3[(μ-SCH2CH2)3N]}3- (D), {[(μ-CO)Fe2(CO)6]3[1,3,5-(μ-SCH2)3C6H3]}3- (E), {[(μ- CO)...