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Supramolecular sensitizer–relay assemblies. An evaluation of binding constants from non‐linear stern–volmer plots
Author(s) -
Boßmann Stefan,
Seiler Martin,
Dürr Heinz
Publication year - 1992
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.610050202
Subject(s) - chemistry , supramolecular chemistry , electron transfer , ruthenium , cationic polymerization , quenching (fluorescence) , electron acceptor , photochemistry , binding constant , calixarene , acceptor , crown ether , excited state , molecule , binding site , polymer chemistry , organic chemistry , fluorescence , catalysis , ion , biochemistry , physics , quantum mechanics , nuclear physics , condensed matter physics
A novel technique for determining the binding constants of host–guest complexes, viz. the bis‐cationic electron relays methylviologen and octylviologen in the macrocyclic host of novel (bisheteroleptic) crown ether‐ruthenium sensitizers, is described. This technique allows the separation of the quenching effects of bound and free electron relays. It can be used to calculate binding constants in non‐covalently linked supramolecular systems evaluating the electron transfer process between guest and host. High binding constants comparable to those in many natural enzymes and the photosynthetic reaction centre were found. As an explanation for the behaviour of the sensitizers bound to the bipyridinium cations it is suggested that photoelectron transfer affects the binding between the excited sensitizer and the bound acceptor.