On the estimation of the strength of supramolecular complexes of fullerenes. Issue 2 (26th July 2018)

• Record Type: Journal Article
• Authors: Denis, Pablo A.
• Other Names: Merino Gabriel guestEditor.; Muñoz‐Castro Alvaro guestEditor.; Chaer Nascimento Marco Antonio guestEditor.; Vela Alberto guestEditor.
• Is Part Of: International journal of quantum chemistry. Volume 119:Issue 2(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2018-07-26
• Subjects: Fullerenes -- Density functional theory -- supramolecular chemistry -- non bonded interactions; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25670
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract : The accurate estimation of the free energy changes in solution for supramolecular complexes is one of the most important challenges for quantum chemistry in this century. In general, there is a good correlation between the association constants determined experimentally and the gas phase binding energies calculated using the most popular density functional methods. However, when the receptors adopt very different structures in the gas and condensed phase, this approach does not work, leading to unreliable predictions. We discuss this problem in detail using three popular fullerene receptors: Aida's dimeric porphyrins, buckycatchers I, and II. We found that it is possible to obtain a reliable order of affinities using gas phase binding energies when a special attention is put on analyzing the structure adopted by the receptor in the gas and condensed phases. Abstract : For rigid fullerene receptors, there is a good correlation between gas phase interaction energies and free energy changes in solutions. However, this is not true for flexible hosts. A proposed solution to this problem is the use of diabatic interaction energies to avoid the inclusion of the host deformation energies.