Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry
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).
- Authors:
-
[1];
[1];
[1];
[1];
[3]
- School of Chemistry, University of Edinburgh, Edinburgh, UK
- Lawrence Berkeley National Laboratory, University of California, Berkeley, USA
- School of Chemistry and EaStCHEM, University of St Andrews, St Andrews, UK
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES), Chemical Sciences, Geosciences & Biosciences Division; Engineering and Physical Sciences Research Council (EPSRC); National Science Foundation (NSF); European Research Council (ERC)
- OSTI Identifier:
- 1580134
- Alternate Identifier(s):
- OSTI ID: 1760200
- Grant/Contract Number:
- AC02-05CH11231; AC02-76SF00515; 740311; EP/L016419/1; EP/N022122/1; EP/M010554/1; CHE-1205189
- Resource Type:
- Published Article
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Name: Dalton Transactions Journal Volume: 49 Journal Issue: 3; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Arnold, Polly L., Wang, Kai, Gray, Steven J., Moreau, Liane M., Booth, Corwin H., Curcio, Massimiliano, Wells, Jordann A. L., and Slawin, Alexandra M. Z. Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9DT03291F.
Arnold, Polly L., Wang, Kai, Gray, Steven J., Moreau, Liane M., Booth, Corwin H., Curcio, Massimiliano, Wells, Jordann A. L., & Slawin, Alexandra M. Z. Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry. United Kingdom. https://doi.org/10.1039/C9DT03291F
Arnold, Polly L., Wang, Kai, Gray, Steven J., Moreau, Liane M., Booth, Corwin H., Curcio, Massimiliano, Wells, Jordann A. L., and Slawin, Alexandra M. Z. Tue .
"Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry". United Kingdom. https://doi.org/10.1039/C9DT03291F.
@article{osti_1580134,
title = {Dicerium letterbox-shaped tetraphenolates: f-block complexes designed for two-electron chemistry},
author = {Arnold, Polly L. and Wang, Kai and Gray, Steven J. and Moreau, Liane M. and Booth, Corwin H. and Curcio, Massimiliano and Wells, Jordann A. L. and Slawin, Alexandra M. Z.},
abstractNote = {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).},
doi = {10.1039/C9DT03291F},
journal = {Dalton Transactions},
number = 3,
volume = 49,
place = {United Kingdom},
year = {Tue Jan 21 00:00:00 EST 2020},
month = {Tue Jan 21 00:00:00 EST 2020}
}
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