A.M. Castilla
Quantification of Stereochemical Communication in Metal–Organic Assemblies
Castilla, A.M.; Miller, M.A.; Nitschke, J.R.; Smulders, M.M.J.
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.
Citation
Castilla, A., Miller, M., Nitschke, J., & Smulders, M. (2016). Quantification of Stereochemical Communication in Metal–Organic Assemblies. Angewandte Chemie International Edition, 55(36), 10616-10620. https://doi.org/10.1002/anie.201602968
Journal Article Type | Article |
---|---|
Acceptance Date | May 3, 2016 |
Online Publication Date | Jun 2, 2016 |
Publication Date | Aug 1, 2016 |
Deposit Date | Jul 12, 2016 |
Publicly Available Date | Aug 23, 2016 |
Journal | Angewandte Chemie International Edition |
Print ISSN | 1433-7851 |
Electronic ISSN | 1521-3773 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 55 |
Issue | 36 |
Pages | 10616-10620 |
DOI | https://doi.org/10.1002/anie.201602968 |
Public URL | https://durham-repository.worktribe.com/output/1407833 |
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Publisher Licence URL
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Copyright Statement
Advance online version © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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