Self-templating and in situ assembly of a cubic cluster-of-clusters architecture based on a {Mo24Fe12} inorganic macrocycle

Xuan, W., Surman, A. J. , Zheng, Q., Long, D.-L. and Cronin, L. (2016) Self-templating and in situ assembly of a cubic cluster-of-clusters architecture based on a {Mo24Fe12} inorganic macrocycle. Angewandte Chemie (International Edition), 55(41), pp. 12703-12707. (doi:10.1002/anie.201603298) (PMID:27358195) (PMCID:PMC5396355)

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Abstract

Engineering self-templating inorganic architectures is critical for the development of bottom-up approaches to nanoscience, but systems with a hierarchy of templates are elusive. Herein we describe that the cluster-anion-templated (CAT) assembly of a {CAT}⊂{Mo24Fe12} macrocycle forms a giant ca. 220 nm3 unit cell containing 16 macrocycles clustered into eight face-shared tetrahedral cluster-of-clusters assemblies. We show that {CAT}⊂{Mo24Fe12} with different CATs gives the compounds 1–4 for CAT=Anderson {FeMo6} (1), Keggin {PMo12} (2), Dawson {P2W18} (3), and {Mo12O36(HPO3)2} (4) polyoxometalates. “Template-free” assembly can be achieved, whereby the macrocycle components can also form a template in situ allowing template to macrocycle to superstructure formation and the ability to exchange the templates. Furthermore, the transformation of template clusters within the inorganic macrocycle {Mo24Fe12} allows the self-generation of an uncapped {Mo12O36(HPO3)2} in compound 4.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Xuan, Mr Weimin and Long, Dr De Liang and Cronin, Professor Leroy and Surman, Dr Andrew and Zheng, Ms Qi
Authors: Xuan, W., Surman, A. J., Zheng, Q., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
Publisher:Wiley
ISSN:1433-7851
ISSN (Online):1521-3773
Published Online:30 June 2016
Copyright Holders:Copyright © 2016 The Authors
First Published:First published in Angewandte Chemie (International Edition) 55(41):12703-12707
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
599451Microscale Chemically Reactive Electronic AgentsLeroy CroninEuropean Commission (EC)FP7 ICT MICRE31CHEM - CHEMISTRY