Premium
Inverse Kinetic and Equilibrium Isotope Effects on Self‐Assembly and Supramolecular Chirality of Porphyrin J‐Aggregates
Author(s) -
Zagami Roberto,
Romeo Andrea,
Castriciano Maria A.,
Monsù Scolaro Luigi
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604675
Subject(s) - porphyrin , kinetic isotope effect , chemistry , chirality (physics) , supramolecular chemistry , inverse , deuterium , enantiomer , supramolecular chirality , kinetic energy , aqueous solution , self assembly , isotope , photochemistry , stereochemistry , crystallography , organic chemistry , crystal structure , physics , quantum mechanics , chiral symmetry , geometry , mathematics , nambu–jona lasinio model , quark
When mixtures of D 2 O/DCl are used to foster the self‐assembly formation of TPPS 4 porphyrin J‐aggregates in aqueous solutions, an inverse kinetic isotope effect of 0.4 and an inverse equilibrium isotope effect of 0.6 are clearly detected. Most importantly, the addition of at least 10 % D 2 O 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.