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.
Highlights
The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported
Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.doi.org/10. 1002/anie.201602968. 2016 The Authors
To emulate the enantioselectivity displayed by enzymes, insights into the conditions under which chiral ligands induce the formation of an enantiopure metal–organic self-assembled capsule are required. Such rules can guide the design of new container molecules offering enantioselective guest binding or catalysis, and may have implications for the understanding of the origin of biological homochirality.[10]
Summary
The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported. We start with the phenomenon of amplification of stereochemical information as previously observed in a FeII4L6 cage with a strong preference to have all metal centers with the same allD configuration.[13] We examine this phenomenon in related tetrahedral cages with different metals, ligand lengths, or geometries (Figure 1).
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