title: Quantification of Stereochemical Communication in Metal-Organic Assemblies.
abstract: The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal-organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per "incorrect" amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra- and inter-vertex coupling constants are used to track the degree of stereochemical communication across a range of metal-organic assemblies (employing different ligands, peripheral amines, and metals); temperature-dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal-organic container molecules.
authors.affiliation: Department of Chemistry University of Cambridge Cambridge CB2 1EW UK.
authors.forename: Ana M
authors.identifier: 0000-0002-5895-6190
authors.initials: AM
authors.lastname: Castilla
authors.affiliation: Department of Chemistry Durham University South Road Durham DH1 3LE UK.
authors.forename: Mark A
authors.identifier: 0000-0002-1403-3343
authors.initials: MA
authors.lastname: Miller
authors.affiliation: Department of Chemistry University of Cambridge Cambridge CB2 1EW UK.
authors.forename: Jonathan R
authors.identifier: 0000-0002-4060-5122
authors.initials: JR
authors.lastname: Nitschke
authors.affiliation: Laboratory of Organic Chemistry Wageningen University Stippeneng 4 6708 WE Wageningen The Netherlands.
authors.forename: Maarten M J
authors.identifier: 0000-0002-6855-0426
authors.initials: MM
authors.lastname: Smulders
keywords: Diastereoselektivität; Käfigverbindungen; Statistische Mechanik; Stereochemische Kommunikation; Supramolekulare Chemie