Exploring the geometric space of metal-organic polyhedrons (MOPs) of metal-oxo clusters

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
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr Deliang and Lee, Mr Edward and Bell, Dr Nicola and Kandasamy, Dr Balamurugan 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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