Inverse kinetic and equilibrium isotopic effect on self-assembly and supramolecular chirality of porphyrin J-aggregates

When mixtures of D2O/DCl are used to foster the self-assembly formation of TPPS4 porphyrin J-aggregates in aqueous solutions, an inverse kinetic isotopic effect of 0.4 and an inverse equilibrium isotopic effect of 0.6 are clearly detected. Most importantly, the addition of at least 10% D2O causes an inversion in the handedness of the final chiral J-aggregates, thus evidencing an important role of deuterium in driving the enantiomeric excess in the scalemic mixture of such supramolecular assemblies.