Protonation of 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphine in Water

Photophysical Properties and Aggregation Behavior of Transition Metal Tetraphenylporphyrin Tetrasulfonate Complexes in Microheterogeneous Media

“…According to the known mechanism [23] (Figure 1), ZnTPPS dissolution in a strongly acidic medium with pH < 2 results in a rapid demetallization of the metal complex (1) …”

The Role of the Counterions in Self-Assembly of J-Aggregates from meso-Aryl Substituted Porphyrin Diacids in Aqueous Solutions

“…[13] The increasing symmetry of the porphyrin diacid (D 2d ) compared to the free base porphyrin (D 2h ) provides the reduced number of the Q-bands because of the excited state degeneracy. [17,18] Besides the significant spectral changes, diprotonation of the chromophore promotes self-assembly of the porphyrin diacid building blocks into the highly-ordered ladder-type supramolecular assemblies known as J-aggregates. [19] However, positive charges of the tectons prevent the porphyrin diacid monomers from direct aggregation, so the formation of the chromophore system capable of coherent excitation requires additional counterions for charge neutralization.…”

“…[3,4] Due to their tendency to ionic and hydrogen bonding of a number of anions and neutral molecules with the nitrogen atoms in the diprotonated porphyrin core, meso-substituted porphyrin diacids are known to function as anionic and molecular receptors. [5][6][7] The macrocycle affinity to various anions leads to the participation of the porphyrin-anion ionic pairs in the selfassembly process providing the basis for its counterion dependence. To date there is a number of papers considering the influence of the counterion nature on the aggregation behavior of meso-tetraphenylporphyrin derivatives.…”

Protonation Equilibriums of Porphin, 5,10,15,20-Tetraphenylporphin, 5,10,15,20-Tetrakis(4’-sulfonatophenyl)­porphin in Methanol

“…Previously we have shown, that formation of aquacomplex [H 4 P ++ (PhSO 3 -) 4 ](H 2 O) 2 is one of the reasons for the synchronous diprotonation of this compound in water (lgK b1 and lgK b2 equal to 4.85 and 4.71, respectively). [5] But the role of the substituents and other medium effects were not determined. Significance of this investigations is determined by the fact, that zwitterions H 4 P ++ (PhSO 3 -) 4 are tectons for pH-controlled ionic self-assembly of porphyrinic J-aggregates and nanotubes on their basis, possessing interesting chemical, optical and electronic properties, which can be applied for developing the nanodevices.…”

“…[1][2][3][4][5] These specific interactions, where the solvent plays the role of a reagent, influences on the result of H 2 P protonation in the solvents of different composition. Previously we have shown, that formation of aquacomplex [H 4 P ++ (PhSO 3 -) 4 ](H 2 O) 2 is one of the reasons for the synchronous diprotonation of this compound in water (lgK b1 and lgK b2 equal to 4.85 and 4.71, respectively).…”