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Photochemical reaction mechanisms and kinetics with molecular nanocrystals: surface quenching of triplet benzophenone nanocrystals
Author(s) -
Simoncelli Sabrina,
Kuzmanich Gregory,
Gard Matthew N.,
GarciaGaribay Miguel A.
Publication year - 2010
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1659
Subject(s) - chemistry , flash photolysis , benzophenone , photochemistry , quenching (fluorescence) , nanocrystal , triplet state , cationic polymerization , solvent , spectroscopy , supramolecular chemistry , kinetics , molecule , chemical engineering , polymer chemistry , organic chemistry , reaction rate constant , fluorescence , physics , quantum mechanics , engineering
Organic molecular nanocrystals suspended in water are useful when studying reactions that occur in the solid state because they retain not only the reactive and supramolecular properties of bulk crystals, but are also amenable to transmission spectroscopy. Having previously studied the triplet state of benzophenone nanocrystals by laser flash photolysis transmission spectroscopy, we now report nanosecond experiments in the presence of several possible quenchers: anionic and cationic surfactants, dissolved oxygen, and as a function of solvent deuteration (H 2 O and D 2 O). After finding these to have no effect, several anionic quenchers (I − , Br − , and N 3 − ) were tested by Stern–Volmer analysis. Significant correlation between the quenching rates in solution and in nanocrystals suggests that the electronic excitation is accessible to quenchers at the surface. Copyright © 2010 John Wiley & Sons, Ltd.