Immobilization of β halogenated ironporphyrin in the silica matrix by the sol–gel process
Immobilization of β halogenated ironporphyrin in the silica matrix by the sol–gel process
复制标题
溶胶-凝胶法将β卤代铁卟啉固定在二氧化硅基质中
DOI：
10.1016/s0022-3093(02)01019-0
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发表时间：
2002
影响因子：
3.5
通讯作者：
Y. Iamamoto
中科院分区：
文献类型：
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作者：
E. A. Vidoto;M. S. Moreira;Fábio S. Vinhado;K. Ciuffi;O. Nascimento;Y. Iamamoto
我们合成了一种有机-无机杂化材料，该材料使用了在meso和β-位均卤化的金属卟啉：铁配合物（5，10，15，20-tetrakis-（pentafluorophenyl）porphine）和（2，3，7，8，12，13，17，18-octa-β-bromo-5，10，15，20-tetrakis-（pentafluorophenyl）porphine），它们稳定了卟啉的氧化降解。以吡啶和咪唑为模板剂，采用溶胶-凝胶法制备固定化载体。（2，3，7，8，12，13，17，18-octa-β-bromo-5，10，15，20-tetrakis-（pentafluorophenyl））卟啉的电子顺磁共振（EPR）谱表明，与溶液体系相比，铁卟啉的包封具有更高的对称性。在咪唑的存在下，观察到铁的还原，通过EPR谱的情况下确定。实验中加入的氯酸蒸气引起铁的氧化，并通过一个轴对称组分检测到少量的高自旋态铁。以碘代苯和过氧化氢为氧供体，铁卟啉对环辛烯的合成具有催化活性。固定化的全卤代卟啉由于其铁的氧化和自旋状态而具有较小的活性。
We present the synthesis and characterization of a hybrid organic–inorganic material using robust metalloporphyrins halogenated in both meso and β-position: the iron complex (5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin and (2,3,7,8,12,13,17,18-octa-β-bromo-5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin, which stabilize the porphyrins against oxidative degradation. The immobilization was developed by the sol–gel process using pyridine and imidazole as template. Electron paramagnetic resonance (EPR) spectra of (2,3,7,8,12,13,17,18-octa-β-bromo-5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin show that the entrapment of ironporphyrin is in a higher symmetry compared to the systems in solution. A reduction of iron was observed in the presence of imidazole, determined by the absence of an EPR spectrum. The addition of chloridric acid vapor induced an oxidation of iron and a small quantity of iron in a high spin state was detected by a component with axial symmetry. The ironporphyrins were active as catalysts for cyclooctene using iodozylbenzene and hydrogen peroxide as oxygen donors. The perhalogenated porphyrins immobilized had a smaller activity due to their iron oxidation and spin states.
DOI：
10.1021/bk-1995-0585
发表时间：
1995-03
期刊：
--
影响因子：
--
作者：
J. E. Mark;C. Y. Lee;P. Bianconi
通讯作者：
J. E. Mark;C. Y. Lee;P. Bianconi