In-situ spectroelectrochemistry (EPR, UV–visible) and aggregation behavior of H2 BDCP and Zn(II)BDCP [BDCP = {5,10,15,20-tetrakis[3,4-(1,4-dioxan)phenyl]porphyrin}2−]

摘要: Abstract In-situ UV–visible and EPR Spectroelectrochemistry of a free base porphyrin, 5,10,15,20-tetrakis[3,4-(1,4-dioxan)phenyl]porphyrin, its zinc derivative, 5,10,15,20-tetrakis[3,4-(1,4-dioxan)phenyl]porphyrinatozinc(II) were performed. On one-electron oxidation the porphyrin in dichloromethane/0.1 M BuN 4 PF 6 using an optically transparent thin layer cell, initial Soret band retains intensity and an equally intense new appears at 453 nm. The Q bands disappear, appear 516, 555 694 nm. At 295 K, it exhibits isotropic signal with peak to separation about 6 G centered g  = 2.004. zinc-porphyrin similar conditions, loses intensity, 466 nm. in-situ generated oxidized species 295 K which is  = 2.0035. formations aggregates/self-assemblies monitored by UV–vis spectroscopy, fluorescence imaging confocal microscope, TEM, SEM DLS measurements. A tentative mechanism has been also proposed for generation different aggregates, varying size shape, water–DMF binary mixtures.