Chasing Weak Forces : Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions
Craen, D. V., Rath, W. H., Huth, M., Kemp, L., Räuber, C., Wollschläger, J., Schalley, C., Valkonen, A., Rissanen, K., & Albrecht, M. (2017). Chasing Weak Forces : Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions. Journal of the American Chemical Society, 139(46), 16959-16966. https://doi.org/10.1021/jacs.7b10098
Published inJournal of the American Chemical Society
© 2017 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
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.
PublisherAmerican Chemical Society
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Research post as Academy Professor, AoF
Additional information about fundingWe are grateful for funding by the international graduate school Seleca (Deutsche Forschungsgemeinschaft) and the Collaborative Research Center 765 (Deutsche Forschungsgemeinschaft), the Academy of Finland (K.R.: grant nos. 263256, 265328, and 292746), and the University of Jyväskylä. We thank Prof. Gerhard Raabe for collection of the data set of Li[Li3(1b)6Ti2].
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