排序方式: 共有47条查询结果,搜索用时 31 毫秒
1.
单核铁(Ⅲ)双卟啉配合物在溶液中的构象平衡及其对环己烷羟化反应的催化活性的影响 总被引:1,自引:0,他引:1
合成及表征了一系列以柔韧碳氢链相连不同长度的p/p型单核铁(Ⅲ)双卟啉配合物,以可见光谱首次观察到该系列配合物在氯仿溶液中开放式及闭合式构象的平衡,发现680nm处吸收峰强度与这种构象平衡有关,烷氧链越长,该吸收峰强度越大.利用该类配合物模拟了细胞色素P450单加氧酶对环己烷的羟化作用,催化结果表明,在以分子氧为氧源及还原剂存在的温和条件下,该类配合物的催化活性显著高于单核铁卟啉(FeTPPCl),随着柔韧碳氢链长度的增加,双卟啉的催化活性依次增加.高的催化活性与双卟啉配合物在溶液中的构象平衡,即闭合式构象引起的立体位阻及电子转移有关. 相似文献
2.
Wang Li Cai Jiwen Mao Zon-Wang Feng Xiao-Long Huang Jin-Wang 《Transition Metal Chemistry》2004,29(4):411-418
Four novel dinickel complexes, coordinated by mixed ligands of tren and racemic amino acids, namely [Ni2(tren)2(dl-alaninato)(H2O)]I3·2H2O (1), [Ni2(tren)2(dl-leucinato)(H2O)]I3·2.5H2O (2), [Ni2(tren)2(dl-phenylalaninato)(H2O)]I3·H2O (3), and {[Ni2(tren)2(dl-histinato)](ClO4)3·1.5H2O}
n
(4), have been synthesized and structurally characterized by X-ray crystallography, FTIR, u.v. and e.s. spectra. They represent the first series of dinickel(II) complexes bridged by the unusual (N,O,O)-coordinated -amino acids. In complexes (1–3), one of the nickel(II) centers is coordinated by four N-atoms of the tren ligand, one O-atom of the carboxylate group of the amino acidato ligand and one H2O molecule. The other nickel(II) center is also coordinated by the four N-atoms of the tren ligand, one carboxylic O-atom and the amino N-atom of the amino acidato ligand, resulting in an asymmetric dinuclear core with chromophores of NiN4O2 and NiN5O. In the polymeric {[Ni2(tren)2(dl-histinato)](ClO4)3·1.5H2O}
n
(4), the imidazole N-atom is also involved in ligation with nickel(II) and both nickel(II) centers have the same chromophore described as NiN5O. The Ni...Ni distances are in the 5.5199(10)–5.5807(15)Å range. Analyses of the magnetic properties of complexes (1), (3) and (4) show that a weak ferromagnetic interaction exists between the two nickel(II) centers. 相似文献
3.
Xiang Ying Shi Jue Lin Ziyang Li Tao Jin-Wang Huang Liang-Nian Ji 《Liquid crystals》2013,40(2):211-214
We observed that the planar aligned nematic liquid crystal (5CB) doped with a volume fraction of 1% of FeTPPCl [5,10,15,20-tetraphenylporphyriniron(III)chloride] or MnTPPCl [5,10,15,20-tetraphenylporphyrinmanganese(III)chloride] dramatically decreased the critical magnetic field for the magnetic field induced Freedericksz transition, while 5CB doped with ZnTPP [5,10,15,20-tetraphenylporphyrinzinc(II)] revealed no such effect, when compared with pure 5CB. In the guest-host (5CB) system, FeTPPCl and MnTPPCl as guests are both strong paramagnetic materials with an interaction through coordination of the -CN group in 5CB onto the metal ion of the porphyrin. As a result, the 5CB molecules are dragged to reorientate under a static magnetic field, while ZnTPP is a diamagnetic material without such a property. This phenomenon concerning magneto-optical components could be useful in liquid crystal displays. 相似文献
4.
Jin-Hua Cai Jin-Wang Huang Ping Zhao Yuan-Jian Ye Han-Cheng Yu Liang-Nian Ji 《Journal of Sol-Gel Science and Technology》2009,50(3):430-436
Three types of novel silica-metalloporphyrins hybrid materials, Si-S-APTCPPFe, Si-S-APTCPPMn and Si-S-APTCPPCo, were prepared
at room temperature by sol–gel method involving a thiol-ene polymerization reaction of 5-(4-allyloxy)phenyl-10,15,20-tri(4-chlorophenyl)porphyrin
(APTCPP) with 3-mercaptopropyltrimethoxysilane (MPS). The hybrid materials were characterized by XRD, SEM, FT–IR, UV–Vis and
TG, and were investigated as catalysts for the aerobic oxidation of cyclohexane. It is found that these hybrid materials are
more efficient catalysts than the analogous non-supported metalloporphyrins for cyclohexane hydroxylation in metalloporphyrin–O2–ascrobate system and the metal ion in the porphyrins significantly affected the catalytic efficiencies of these hybrid materials. 相似文献
5.
Jia-Zheng Lu Yi-fan Du Bin Wu Jin-Wang Huang Jing Jiang 《Transition Metal Chemistry》2010,35(4):451-456
A fluorescein–porphyrin hybrid (Fl-PTPP) has been synthesized and characterized by UV/Vis, IR, 1H NMR, ES-MS and elemental analysis. The supramolecular self-assembly of Fl-PTPP with the copper(II) complex of 5-(p-amino-phenyl)-10,15,20-triphenylporphyrin, (CuAPTPP), by hydoxyl-amino type hydrogen bonding was studied using vapor pressure
osmometry (VPO) measurements, ES-MS, UV/Vis, 1H NMR and fluorescence spectroscopic titration. The data indicate formation of a (Fl-PTPP)–CuAPTPP supramolecular complex.
Fluorescence strengthening character was observed in a spectroscopic titration experiment for the Fl-PTPP/CuAPTPP system.
The association constant of the supramolecular complex was calculated from the fluorescence titration data, and found to be
less than that of a carboxyl–carboxyl type hydrogen-bonding system. 相似文献
6.
利用激子旋转扩散理论研究了一类低掺杂卟啉侧链聚合物中卟啉侧链基团的旋转对其发光动力学过程的影响.研究表明,卟啉侧链基团的旋转行为是导致激发态无辐射能量弛豫的重要途径.基团旋转越容易,能量弛豫速度越快,这可导致一个快速的荧光衰变动力学过程.在卟啉低掺杂浓度和聚合物分子链间距离较大的情况下,卟啉侧链基团的旋转成为影响荧光寿命和发光效率的主要因素.对实验测得的两种样品的荧光弛豫过程进行了拟合,理论结果与实验结果符合较好.
关键词:
激子旋转弛豫
瞬态荧光
卟啉侧链聚合物 相似文献
7.
8.
9.
通过采用时间分辨荧光光谱技术测量了一种卟啉侧链聚合物薄膜:卟啉丙烯酸酯-苯乙烯共聚物poly[porphyrin acrylate-styrene] (P[(por)A-S])在高激发密度下的瞬态荧光特性.实验发现,P[(por)A-S]样品的荧光衰减随聚合物分子浓度的增大而加快.利用Frster机制的双分子猝灭理论对其浓度猝灭的原因进行了分析,理论结果与实验结果符合较好.研究表明,在高激发密度的情况下,Frster机制的双分子作用是加快卟啉侧链聚合物初始荧光衰减和降低其发光效率的主要因素. 相似文献
10.
Cai Jin-Hua Ye Yuan-Jian Huang Jin-Wang Yu Han-Cheng Ji Liang-Nian 《Journal of Sol-Gel Science and Technology》2012,62(3):432-440
Three types of silica gel supported titanium dioxide particles immobilizing Zn(II) carboxylphenyl porphyrins appending p-CH3, p-H and p-Cl phenyl substituents (designated as ZnMP–TiO2–SiO2, ZnPP–TiO2–SiO2 and ZnCP–TiO2–SiO2, respectively) have been synthesized and characterized using SEM, XRD, IR, AFS, DRS, UV–Vis, XPS and TG. The photodegradation
of α-terpinene in aqueous suspension was used to determine the photocatalytic activity of TiO2–SiO2 samples which had been impregnated with Zn(II) porphyrins, as sensitizers. The experimental results confirmed that the photocatalytic
activitys of these composites are much higher than those of the nonmodified TiO2–SiO2 under visible light irradiation and follow the order of ZnMP–TiO2–SiO2 > ZnPP–TiO2–SiO2 > ZnCP–TiO2–SiO2. 相似文献