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Dicerium letterbox-shaped tetraphenolates : f-block complexes designed for two-electron chemistry

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Arnold_2019_DT_Dicerium_CC.pdf (1.972Mb)
Date
21/01/2020
Author
Arnold, Polly L.
Wang, Kai
Gray, Steven J.
Moreau, Liane M.
Booth, Corwin H.
Curcio, Massimiliano
Wells, Jordann A. L.
Slawin, Alexandra M. Z.
Keywords
QD Chemistry
DAS
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Abstract
Rare examples of molecular, dinuclear CeIII and PrIII complexes with robust Ln-coordination are accessible by use of the tetraphenolate pTP as a supporting, chelating O-donor ligand platform, pTP = [{2-(OC6H2R2-2,4)2CH}-C6H4-1,4]4− that favours the higher formal oxidation states accessible to rare earths. Two classes of complexes have been made from the platforms; one metallacyclic 2 + 2 [Ln2(pTP)2] framework with a rigid, letterbox-shaped geometry and [Ln(aryloxide)4] core, and one more flexible [(LnX)2(pTP)] with one rare earth ion at either end of the platform. The LnIII letterbox complexes have two K+ counter-cations, one of which sits inside the letterbox, binding the two central arenes of the platform sufficiently strongly that it cannot be displaced by solvent molecules (THF and pyridine) or crown ethers. Oxidation of the CeIII lettterboxes is facile and forms the unusual neutral molecular (CeIV)2 letterbox in which the CeIV reduction potential is −1.83 V vs. Fc/Fc+. The electronic structure of the Ce(III/IV) complexes was investigated using HERFD-XAS (high energy resolution fluorescence detection X-ray absorption spectroscopy).
Citation
Arnold , P L , Wang , K , Gray , S J , Moreau , L M , Booth , C H , Curcio , M , Wells , J A L & Slawin , A M Z 2020 , ' Dicerium letterbox-shaped tetraphenolates : f-block complexes designed for two-electron chemistry ' , Dalton Transactions , vol. 49 , no. 3 , pp. 877-884 . https://doi.org/10.1039/c9dt03291f
Publication
Dalton Transactions
Status
Peer reviewed
DOI
https://doi.org/10.1039/c9dt03291f
ISSN
1477-9226
Type
Journal article
Rights
Copyright © 2019 The Author(s). Open Access Article. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/19436

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