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Thermodynamics of induced-fit binding inside polymacrocyclic porphyrin hosts
Ist Teil von
Journal of the American Chemical Society, 1990-07, Vol.112 (15), p.5780-5789
Ort / Verlag
Washington, DC: American Chemical Society
Erscheinungsjahr
1990
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
The binding of bis-amine ligands to a series of cyclic zinc porphyrin dimers has been characterized by NMR and electronic spectroscopy. The cavity within the flexible dimers is kept closed by {pi}-{pi} interactions between the porphyrin and aromatic bridging groups but can be opened by ligands whose binding is strong enough to overcome this energetic barrier. Analysis of the binding of these bifunctional and the corresponding monofunctional ligands to the porphyrin dimers and corresponding monomeric porphyrins allowed definition of the parameters {Delta}{Delta}G, {Delta}{Delta}H, and {Delta}{Delta}S. These are specifically associated with the energetic costs of conformational switching and yield information about the strength of the {pi}-{pi} interactions that hold the cavity closed.