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Photon Funnels for One-Way Energy Transfer: Multimetallic Assemblies Incorporating Cyclometallated Iridium or Rhodium Units Accessed by Sequential Cross-Coupling and Bromination

Knuckey, Kathryn J.; Williams, J.A. Gareth

Photon Funnels for One-Way Energy Transfer: Multimetallic Assemblies Incorporating Cyclometallated Iridium or Rhodium Units Accessed by Sequential Cross-Coupling and Bromination Thumbnail


Authors

Kathryn J. Knuckey



Abstract

The generation of multimetallic assemblies is a widely explored theme, owing to the relevance of controlling energy and electron transfer between metal centres to many fields of contemporary importance. Boronic acid substituted coordination and organometallic complexes have been shown to be useful synthons in the formation of such structures through cross-coupling with halogenated complexes. In this work we used such a methodology to generate an octanuclear mixed-metal compound of composition Ir7Ru having a dendrimer wedge-like structure. The method combined cross-coupling with regiospecific bromination of phenylpyridine (ppy) ligands at the position para to the C–Ir bond. The propensity of Ir(ppy)2-based complexes to electrophilic bromination was found to be deactivated by the introduction of fluorine atoms. The coupling methodology was extended to rhodium-containing systems, exemplified by a tetranuclear system of composition Rh2Ir1Ru1. The synthesis required the use of boronic acid appended RhIII complexes, which could be accessed by the introduction of a neopentyl boronate ester appended bipyridine into the coordination sphere of RhIII. The excited-state energies of the constituent metal units in the resulting multinuclear complexes are such that unidirectional energy transfer occurs from the RhIII/IrIII branches to the RuII core. The luminescence thus resembles that of an isolated [Ru(bpy)3]2+ unit, but the ability of the structure to collect light is greatly enhanced.

Citation

Knuckey, K. J., & Williams, J. G. (2017). Photon Funnels for One-Way Energy Transfer: Multimetallic Assemblies Incorporating Cyclometallated Iridium or Rhodium Units Accessed by Sequential Cross-Coupling and Bromination. European Journal of Inorganic Chemistry, 2017(44), 5205-5214. https://doi.org/10.1002/ejic.201701020

Journal Article Type Article
Acceptance Date Sep 25, 2017
Online Publication Date Oct 19, 2017
Publication Date Dec 1, 2017
Deposit Date Oct 20, 2017
Publicly Available Date Oct 19, 2018
Journal European Journal of Inorganic Chemistry
Print ISSN 1434-1948
Electronic ISSN 1099-0682
Publisher Wiley-VCH Verlag
Peer Reviewed Peer Reviewed
Volume 2017
Issue 44
Pages 5205-5214
DOI https://doi.org/10.1002/ejic.201701020

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Copyright Statement
This is the peer reviewed version of the following article: Knuckey, K. J. and Williams, J. A. G. (2017), Photon Funnels for One-Way Energy Transfer: Multimetallic Assemblies Incorporating Cyclometallated Iridium or Rhodium Units Accessed by Sequential Cross-Coupling and Bromination. European Journal of Inorganic Chemistry, 2017(44): 5205-5214, which has been published in final form at https://doi.org/10.1002/ejic.201701020. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.







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