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Quantification of Stereochemical Communication in Metal–Organic Assemblies

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 optica...

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Autores principales: Castilla, Ana M., Miller, Mark A., Nitschke, Jonathan R., Smulders, Maarten M. J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5012202/
https://www.ncbi.nlm.nih.gov/pubmed/27656004
http://dx.doi.org/10.1002/ange.201602968
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author Castilla, Ana M.
Miller, Mark A.
Nitschke, Jonathan R.
Smulders, Maarten M. J.
author_facet Castilla, Ana M.
Miller, Mark A.
Nitschke, Jonathan R.
Smulders, Maarten M. J.
author_sort Castilla, Ana M.
collection PubMed
description 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.
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spelling pubmed-50122022016-09-19 Quantification of Stereochemical Communication in Metal–Organic Assemblies Castilla, Ana M. Miller, Mark A. Nitschke, Jonathan R. Smulders, Maarten M. J. Angew Chem Weinheim Bergstr Ger Zuschriften 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. John Wiley and Sons Inc. 2016-06-02 2016-08-26 /pmc/articles/PMC5012202/ /pubmed/27656004 http://dx.doi.org/10.1002/ange.201602968 Text en © 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 (http://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Zuschriften
Castilla, Ana M.
Miller, Mark A.
Nitschke, Jonathan R.
Smulders, Maarten M. J.
Quantification of Stereochemical Communication in Metal–Organic Assemblies
title Quantification of Stereochemical Communication in Metal–Organic Assemblies
title_full Quantification of Stereochemical Communication in Metal–Organic Assemblies
title_fullStr Quantification of Stereochemical Communication in Metal–Organic Assemblies
title_full_unstemmed Quantification of Stereochemical Communication in Metal–Organic Assemblies
title_short Quantification of Stereochemical Communication in Metal–Organic Assemblies
title_sort quantification of stereochemical communication in metal–organic assemblies
topic Zuschriften
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5012202/
https://www.ncbi.nlm.nih.gov/pubmed/27656004
http://dx.doi.org/10.1002/ange.201602968
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