Kinetic Investigation on Tetrakis(4-Sulfonatophenyl)Porphyrin J-Aggregates Formation Catalyzed by Cationic Metallo-Porphyrins.

Under mild acidic conditions, various metal derivatives of tetrakis(4--methylpyridinium)porphyrin (gold(III), AuT; cobalt(III), CoT; manganese(III), MnT and zinc(II), ZnT) catalytically promote the supramolecular assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (HTPPS) into J-aggregates. The aggregation kinetics have been treated according to a well-established model that involves the initial formation of a critical nucleus containing porphyrin units, followed by autocatalytic growth, in which the rate evolves as a power of time. An analysis of the extinction time traces allows to obtain the rate constants for the auto-catalyzed pathway, , and the number of porphyrins involved in the initial seeding.

Controlling J-Aggregates Formation and Chirality Induction through Demetallation of a Zinc(II) Water Soluble Porphyrin.

Under acidic conditions and at high ionic strength, the zinc cation is removed from its metal complex with 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) thus leading to the diacid free porphyrin, that subsequently self-organize into J-aggregates. The kinetics of the demetallation step and the successive supramolecular assembly formation have been investigated as a function of pH and ionic strength (controlled by adding ZnSO). The demetallation kinetics obey to a rate law that is first order in [ZnTPPS] and second order in [H], according to literature, with = 5.

Aggregates of a cationic porphyrin as supramolecular probes for biopolymers.

The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe.

Linear and circular dichroism in porphyrin J-aggregates probed by polarization modulated scanning near-field optical microscopy.

Polarization modulated scanning near-field optical microscopy (PM-SNOM) is effective in detecting circular and linear dichroism with sub-wavelength resolution. PM-SNOM investigation of the chiroptical properties of single ribbon-like nanosized J-aggregates formed by acid induced aggregation of tris-(4-sulfonatophenyl)phenylporphyrin is reported. Linear dichroism maps give evidence of well-organized chromophores packed in linear arrays within the structure of the nanoribbons.