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Stepwise Effective Molarities in Porphyrin Oligomer Complexes: Preorganization Results in Exceptionally Strong Chelate Cooperativity

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Hannah J. Hogben, Johannes K. Sprafke, Markus Hoffmann, Miłosz Pawlicki, and Harry L. Anderson*

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, United Kingdom

J. Am. Chem. Soc., 2011, 133 (51), pp 20962–20969

DOI: 10.1021/ja209254r

Publication Date (Web): November 17, 2011

harry.anderson@chem.ox.ac.uk

Section:

Phase Equilibriums, Chemical Equilibriums, and Solutions

Abstract

Complexes of zinc porphyrin oligomers with multivalent ligands can be denatured by adding a large excess of a monodentate ligand, such as quinuclidine. We have used denaturation titrations to determine the stabilities of the complexes of a cyclic zinc–porphyrin hexamer with multidentate ligands with two to six pyridyl coordination sites. The corresponding complexes of linear porphyrin oligomers were also investigated. The results reveal that the stepwise effective molarities (EMs) for the third through sixth intramolecular coordination events with the cyclic hexamer are extremely high (EM = 10²–10³ M), whereas the values for the linear porphyrin oligomers are modest (EM ≈ 0.05 M). The speciation profiles for the denaturation reactions demonstrate that intermediate species are not significantly populated and that these equilibria are well described by a highly cooperative two-state model.

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History

Published In Issue December 28, 2011
Article ASAPDecember 06, 2011
Just Accepted ManuscriptNovember 17, 2011
Received: October 01, 2011

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Stepwise Effective Molarities in Porphyrin Oligomer Complexes: Preorganization Results in Exceptionally Strong Chelate Cooperativity