Porphyrin/calixarene self-assemblies in aqueous solution

摘要: Abstract The variations of calix[4]arene linkages between phenolic units and the cationic substituents on porphyrin periphery affect modes interaction photophysical parameters porphyrin/calixarene complexes. 5,10,15,20-Tetrakis( N- methylpyridinium-2-yl)porphyrin (TMPyP2) forms stable complexes with tetrasulfonated calix[4]arene, thiacalix[4]arene sulfonylcalix[4]arene 1:1 stoichiometry binding constants above 10 6 , (9.3 ± 0.9) × 10 5 (8.3 ± 0.8) × 10 4  M −1 respectively. We suggest that quenching singlet triplet states TMPyP2 involves fast electron transfer excited phenolates. Surprisingly, both 5,10,15,20-tetrakis( methylpyridinium-4-yl)porphyrin (TMPyP4) 5,10,15,20-tetrakis(4-trimethylammoniophenyl)porphyrin (TMAPP) behave differently. After calixarenes nonspecific extended self-assemblies a random arrangement are formed as confirmed by UV–vis, fluorescence spectroscopy, AFM, microscopy light scattering techniques. TMPyP4/calix[4]arene system is exception because components form molecular complex stoichiometry. quickly transformed into self-assembly at higher TMPyP4 concentrations.