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This paper presents an attempt to separate the effect of the additive parameters of the reaction medium (the acidity and the ionic strength of the solution) and specific factors, such as the nature of the counterions and the presence of different binding agents and templating molecules, on self-assembly of meso-aryl-substituted porphyrin in acidic aqueous solutions. The studies reveal the importance of the specific intermolecular interactions that determine the structural, and hence, photophysical properties of the multiporphyrin arrays, as well as the kinetics of self-assembly. The particular attention in this paper is paid to the influence of the counterions on aggregation behaviour of a number of tetraphenylporphyrin derivatives, as well as to their role in J-aggregate structure stabilization. The results obtained can be applied for the development of the novel ways for design and synthesis of various supramolecular systems on the basis of diprotonated porphyrins with definite structure and desired properties for nonlinear optics and sensor applications.

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