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

Article Article scientifique Article Neutral Heteroleptic Lanthanide Complexes for Unravelling Host–Guest Assemblies in Organic Solvents: The Law of Mass Action Revisited eng 2020 author Baudet Karine 751441 author Kale Vishal Sopanrao 865186 author Mirzakhani Mohsen 867142 author Babel Lucille author Naseri Soroush 906987 author Besnard Céline 682138 author Nozary Homayoun 86105 author Piguet Claude 0000-0001-7064-8548 22415 62-75 10.1021/acs.inorgchem.9b00755 0020-1669 https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.9b00755 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. Dewey 540 Swiss National Science Foundation Can Functional Metallopolymers and Supramolecular Assemblies Benefit from Molecular Organization Mastered by Coordination Chemists ? 178758 CH Project funding 40 Département de chimie minérale, analytique et appliquée 145 false 774 Groupe Piguet Inorganic Chemistry 59 1 85e49ddf-6232-48c8-b641-005981735106 Article (Accepted version) Public Neutral_Heteroleptic_Lanthanide_01_20.pdf 1526384 application/pdf Restricted 2020-05-13 4c57148f-2775-4909-b64e-12ed1d4deecb Article (Published version) Restricted acs.inorgchem.9b00755.pdf 3211387 application/pdf openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie minérale, analytique et appliquée

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Neutral Heteroleptic Lanthanide Complexes for Unravelling Host–Guest Assemblies in Organic Solvents: The Law of Mass Action Revisited	Inorganic Chemistry			2020	493	398

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Kale, Vishal Sopanrao