Synthetic considerations in the self-assembly of coordination polymers of pyridine-functionalised hybrid Mn-Anderson polyoxometalates

Yazigi, F.-J., Wilson, C. , Long, D.-L. and Forgan, R. S. (2017) Synthetic considerations in the self-assembly of coordination polymers of pyridine-functionalised hybrid Mn-Anderson polyoxometalates. Crystal Growth and Design, 17(9), pp. 4739-4748. (doi: 10.1021/acs.cgd.7b00672)

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The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilised, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups towards linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn2+ and Cu2+ link pyridine-appended Mn-Anderson clusters into two- and three-dimensional network solids with complex connectivities and topologies. Careful inspection of their solid-state structures has allowed us to identify common structure-directing features across these coordination polymers, including a square motif where two Zn2+ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, co-ligands and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Yazigi, Francois-joseph and Wilson, Dr Claire and Forgan, Professor Ross and Long, Dr Deliang
Authors: Yazigi, F.-J., Wilson, C., Long, D.-L., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Crystal Growth and Design
Publisher:American Chemical Society
ISSN (Online):1528-7505
Published Online:19 July 2017
Copyright Holders:Copyright © 2017 American Chemical Society
First Published:First published in Crystal Growth and Design 17(9):4739–4748
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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