Chasing Weak Forces: Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions.

Autor:	Van Craen D; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany., Rath WH; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany., Huth M; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany., Kemp L; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany., Räuber C; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany., Wollschläger JM; Institut für Chemie und Biochemie-Organische Chemie, Freie Universität Berlin , Takustrasse 3, Berlin 14195, Germany., Schalley CA; Institut für Chemie und Biochemie-Organische Chemie, Freie Universität Berlin , Takustrasse 3, Berlin 14195, Germany., Valkonen A; Department of Chemistry, Nanoscience Center, University of Jyvaskyla , Survontie 9 B, Jyväskylä 40014, Finland., Rissanen K; Department of Chemistry, Nanoscience Center, University of Jyvaskyla , Survontie 9 B, Jyväskylä 40014, Finland., Albrecht M; Institut für Organische Chemie, RWTH Aachen University , Landoltweg 1, Aachen 52074, Germany.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2017 Nov 22; Vol. 139 (46), pp. 16959-16966. Date of Electronic Publication: 2017 Nov 08.
DOI:	10.1021/jacs.7b10098
Abstrakt:	London dispersion forces are the weakest interactions between molecules. Because of this, their influence on chemical processes is often low, but can definitely not be ignored, and even becomes important in cases of molecules with large contact surfaces. Hierarchically assembled dinuclear titanium(IV) helicates represent a rare example in which the direct observation of London dispersion forces is possible in solution even in the presence of strong cohesive solvent effects. Hereby, the dispersion forces do not unlimitedly support the formation of the dimeric complexes. Although they have some favorable enthalpic contribution to the dimerization of the monomeric complex units, large flexible substituents become conformationally restricted by the interactions leading to an entropic disadvantage. The dimeric helicates are entropically destabilized.
Databáze:	MEDLINE
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