Relationship between chemical structure and supramolecular effective molarity for formation of intramolecular H-bonds

SUN, Hongmei, HUNTER, Christopher A., NAVARRO, Cristina and TUREGA, Simon (2013). Relationship between chemical structure and supramolecular effective molarity for formation of intramolecular H-bonds. Journal of the American Chemical Society, 135 (35), 13129-13141.

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Official URL: http://dx.doi.org/10.1021/ja406235d
Link to published version:: 10.1021/ja406235d

Abstract

Effective molarity (EM) is a key parameter that determines the efficiency of a range of supramolecular phenomena from the folding of macromolecules to multivalent ligand binding. Coordination complexes formed between zinc porphyrins equipped H-bond donor sites and pyridine ligands equipped with H-bond acceptor sites have allowed systematic quantification of EM values for the formation of intramolecular H-bonds in 240 different systems. The results provide insights into the relationship of EM to supramolecular architecture, H-bond strength, and solvent. Previous studies on ligands equipped with phosphonate diester and ether H-bond acceptors were inconclusive, but the experiments described here on ligands equipped with phosphine oxide, amide, and ester H-bond acceptors resolve these ambiguities. Chemical double-mutant cycles were used to dissect the thermodynamic contributions of individual H-bond interactions to the overall stabilities of the complexes and hence determine the values of EM, which fall in the range 1–1000 mM. Solvent has little effect on EM, and the values measured in toluene and 1,1,2,2-tetrachloroethane are similar. For H-bond acceptors that have similar geometries but different H-bond strengths (amide and ester), the values of EM are very similar. For H-bond acceptors that have different geometries but similar H-bond strengths (amide and phosphonate diester), there is little correlation between the values of EM. These results imply that supramolecular EMs are independent of solvent and intrinsic H-bond strength but depend on supramolecular architecture and geometric complementarity.

Item Type: Article
Additional Information: Publication Date (Web): August 21, 2013
Research Institute, Centre or Group: Biomolecular Sciences Research Centre
Identification Number: 10.1021/ja406235d
Depositing User: Jamie Young
Date Deposited: 30 Jun 2015 13:18
Last Modified: 30 Jun 2015 13:18
URI: http://shura.shu.ac.uk/id/eprint/10012

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