Expanding Coefficient: A Parameter To Assess the Stability
of Induced-Fit Complexes

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Abstract

Here we propose a new parameter, the Expanding Coefficient (EC), that can be correlated with the thermodynamic stability of supramolecular complexes governed by weak secondary interactions and obeying the induced-fit model. The EC values show a good linear relationship with the log K _app of the respective pseudorotaxane complexes investigated. According to Cram’s Principle of Preorganization, the EC can be considered an approximate mechanical measure of the host’s reorganization energy cost upon adopting the final bound geometry.

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Most cited references 54

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Semiempirical GGA-type density functional constructed with a long-range dispersion correction.

Stefan Grimme (2006)

A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C(6) x R(-6). A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common density functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on standard thermochemical benchmark sets, for 40 noncovalently bound complexes, including large stacked aromatic molecules and group II element clusters, and for the computation of molecular geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for standard functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean absolute deviation of only 3.8 kcal mol(-1). The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the average CCSD(T) accuracy. The basic strategy in the development to restrict the density functional description to shorter electron correlation lengths scales and to describe situations with medium to large interatomic distances by damped C(6) x R(-6) terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chemical method for large systems where dispersion forces are of general importance. Copyright 2006 Wiley Periodicals, Inc.

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The Design of Molecular Hosts, Guests, and Their Complexes (Nobel Lecture)

Donald J. Cram (1988)

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The 55 % Solution: A Formula for Molecular Recognition in the Liquid State

Sandro Mecozzi, Julius Rebek, Jr. (1998)

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Author and article information

Journal

Journal ID (nlm-ta): Org Lett

Journal ID (iso-abbrev): Org Lett

Journal ID (publisher-id): ol

Journal ID (coden): orlef7

Title: Organic Letters

Publisher: American Chemical Society

ISSN (Print): 1523-7060

ISSN (Electronic): 1523-7052

Publication date (Electronic): 16 February 2021

Publication date (Print): 05 March 2021

Volume: 23

Issue: 5

Pages: 1804-1808

Affiliations

[† ]Dipartimento di Chimica e Biologia “A. Zambelli”, Università di Salerno , via Giovanni Paolo II, 132, I-84084, Fisciano (Salerno), Italy

[‡ ]Dipartimento di Scienze del Farmaco e della Salute, Università di Catania , viale Andrea Doria, 6, I-95125 Catania, Italy

[§ ]Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST) , Av. Països Catalans, 16, 43007 Tarragona, Spain

Author notes

[* ]E-mail: ctalotta@ 123456unisa.it .

[* ]E-mail: arescifina@ 123456unict.it .

[* ]E-mail: pballester@ 123456iciq.es .

[* ]E-mail: neri@ 123456unisa.it .

Article

DOI: 10.1021/acs.orglett.1c00165

PMC ID: 8028309

PubMed ID: 33591765

SO-VID: ed99c28e-5c41-402d-b4e4-46519a624f37

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Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

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Date received : 20 January 2021

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ScienceOpen disciplines: Organic & Biomolecular chemistry

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ScienceOpen disciplines: Organic & Biomolecular chemistry

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Expanding Coefficient: A Parameter To Assess the Stability of Induced-Fit Complexes

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Most cited references 54

Semiempirical GGA-type density functional constructed with a long-range dispersion correction.

The Design of Molecular Hosts, Guests, and Their Complexes (Nobel Lecture)

The 55 % Solution: A Formula for Molecular Recognition in the Liquid State

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