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Neutral Heteroleptic Lanthanide Complexes for Unravelling Host–Guest Assemblies in Organic Solvents: The Law of Mass Action Revisited

Published inInorganic Chemistry, vol. 59, no. 1, p. 62-75
Publication date2020
Abstract

The binding of lanthanide containers [Ln(-diketonate)3dig] (dig = 1-methoxy-2-(2- methoxyethoxy)ethane) to aromatic tridentate N-donor ligands (L) in dichloromethane produces neutral nine-coordinate heteroleptic [LLn(-diketonate)3] complexes, the equilibrium reaction quotients of which vary with the total concentrations of the reacting partners. This problematic drift prevents the determination of both reliable thermodynamic stability constants and intrinsic host-guest affinities. The classical solution theory assigns this behavior to changes in the activity coefficients of the various partners in non-ideal solutions and a phenomenological approach attempts to quantitatively attribute this effect to some partition of the solvent molecules between bulk-innocent and contact-non-innocent contributors to the chemical potential. This assumption eventually predicts an empirical linear dependence of the equilibrium reaction quotient on the concentration of the formed [LLn(-diketonate)3] complexes, a trend experimentally supported in this contribution for various ligands L differing in lipophilicity and nuclearity and for lanthanide containers grafted with diverse beta-diketonate co-ligands. Even if the origin of the latter linear dependence is still the subject of debate, this work demonstrates that this approach can be exploited by experimentalists for extracting reliable thermodynamic constants suitable for analyzing and comparing host-guest affinities in organic solvents.

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Citation (ISO format)
BAUDET, Karine et al. Neutral Heteroleptic Lanthanide Complexes for Unravelling Host–Guest Assemblies in Organic Solvents: The Law of Mass Action Revisited. In: Inorganic Chemistry, 2020, vol. 59, n° 1, p. 62–75. doi: 10.1021/acs.inorgchem.9b00755
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ISSN of the journal0020-1669
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