Kandasamy, B., Lee, E. , Long, D.-L. , Bell, N. and Cronin, L. (2021) Exploring the geometric space of metal-organic polyhedrons (MOPs) of metal-oxo clusters. Inorganic Chemistry, 60(19), pp. 14772-14778. (doi: 10.1021/acs.inorgchem.1c01987) (PMID:34549944) (PMCID:PMC8493551)
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Abstract
Metal organic polyhedra (MOPs) such as coordination cages and clusters are increasingly utilized across many fields, but their geometrically selective assembly during synthesis is nontrivial. When ligand coordination along these polyhedral edges is arranged in an unsymmetrical mode or the bridging ligand itself is nonsymmetric, a vast combinatorial space of potential isomers exists complicating formation and isolation. Here we describe two generalizable combinatorial methodologies to explore the geometrical space and enumerate the configurational isomers of MOPs with discrimination of the chiral and achiral structures. The methodology has been applied to the case of the octahedron {Bi6Fe13L12} which has unsymmetrical coordination of a carboxylate ligand (L) along its edges. For these polyhedra, the enumeration methodology revealed 186 distinct isomers, including 74 chiral pairs and 38 achiral. To explore the programming of these, we then used a range of ligands to synthesize several configurational isomers. Our analysis demonstrates that ligand halo-substituents influence isomer symmetry and suggests that more symmetric halo-substituted ligands counterintuitively yield lower symmetry isomers. We performed mass spectrometry studies of these {Bi6Fe13L12} clusters to evaluate their stability and aggregation behavior in solution and the gas phase showing that various isomers have different levels of aggregation in solution.
Item Type: | Articles |
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Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Lee, Mr Eddy and Bell, Dr Nicola and Kandasamy, Dr Balamurugan and Long, Dr Deliang and Cronin, Professor Lee |
Authors: | Kandasamy, B., Lee, E., Long, D.-L., Bell, N., and Cronin, L. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Inorganic Chemistry |
Publisher: | American Chemical Society |
ISSN: | 0020-1669 |
ISSN (Online): | 1520-510X |
Published Online: | 22 September 2021 |
Copyright Holders: | Copyright © 2021 American Chemical Society |
First Published: | First published in Inorganic Chemistry 60(19): 14772-14778 |
Publisher Policy: | Reproduced under a Creative Commons licence |
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