화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.110, No.14, 7309-7315, 2006
Counteranion dependent protonation and aggregation of tetrakis(4-sulfonatophenyl)porphyrin in organic solvents
The tetrabutylammonium salt of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) is soluble in dichloromethane, and the general properties of this compound have been investigated as function of various added acids HX (X = Cl, Br, I,CF3COO, CF3SO3, TFPB) through UV-vis absorption spectroscopy, steady state fluorescence emission, and resonance light-scattering (RLS) techniques. Upon addition of HX, the initial monomeric free base TPPS is readily converted in an aggregated species, whose spectroscopic features are independent of the nature of the counteranion X. All the spectroscopic evidence suggest a J-type arrangement of chromophores in this aggregate, involving strong hydrogen bonds, electrostatic, and dispersive interactions. In the specific case of chloride and bromide, in the presence of a TBAX excess, the addition of the corresponding acid leads to a monomeric ion-pair between the TBA cations and the diacid TPPS, whose central core is strongly interacting with the halide. On further increasing the acid concentration in these latter solutions, fully protonated species are formed that eventually start to aggregate.