Supramolecular conformational effects in the electrocatalytic properties of electrostatic assembled films of meso(3-and 4-pyridyl) isomers of tetraruthenated porphyrins

被引:30
|
作者
Mayer, I
Eberlin, MN
Tomazela, DM
Toma, HE
Araki, K [1 ]
机构
[1] Univ Sao Paulo, Inst Quim, BR-05513970 Sao Paulo, Brazil
[2] Univ Estadual Campinas, Inst Quim, BR-13083970 Campinas, SP, Brazil
关键词
supramolecular chemistry; metalloporphyrins; electrostatic assembled films; electrocatalysis; electrochemistry; mass spectrometry;
D O I
10.1590/S0103-50532005000300016
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Meso(3- and 4-pyridyl) porphyrins coordinated to four [Ru( bipy)(2) Cl](+) complexes, M(3-TRPyP) or M(4-TRPyP), where M=2H(+) and Zn2+, have been obtained and characterized by electrochemistry, spectroscopy and mass spectrometry. Layer-by-layer electrostatic assembled films with tetrasulfonated phthalocyaninatecuprate(II) anion, CuTSPc, displayed distinct electrocatalytic activity towards sulfite and nitrite oxidation. In general, the films derived from the M(4-TRPyP) isomers are more effective for the oxidation of nitrite, whereas those containing the M(3-TRPyP) isomers are more efficient for the oxidation of sulfite. The results demonstrated the influence of molecular geometry on the active sites of porphyrinic nanomaterials, enhancing the electron-transfer process in the M(3-TRPyP) derivative. This effect results from changes in the chemical environment around the active sites, induced by the contrasting molecular packing interactions with CuTSPc.
引用
收藏
页码:418 / 425
页数:8
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