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Cooperativity in the self-assembly of porphyrin ladders.


ABSTRACT: Cooperativity is a general feature of intermolecular interactions in biomolecular systems, but there are many different facets of the phenomenon that are not well understood. Positive cooperativity stabilizes a system as progressively more interactions are added, and the origin of the beneficial free energy may be entropic or enthalpic in origin. An "enthalpic chelate effect" has been proposed to operate through structural tightening that improves all of the functional group interactions in a complex, when it is more strongly bound. Here, we present direct calorimetric evidence that no such enthalpic effects exist in the cooperative assembly of supramolecular ladder complexes composed of metalloporphyrin oligomers coordinated to bipyridine ligands. The enthalpic contributions of the indivi

SUBMITTER: Camara-Campos A 

PROVIDER: S-EPMC1413879 | biostudies-literature | 2006 Feb

REPOSITORIES: biostudies-literature