Heteroleptic samarium(III) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy

Goodwin, C. A.P., Réant, B. L.L., Kragskow, J. G.C., DiMucci, I. M., Lancaster, K. M., Mills, D. P. and Sproules, S. (2018) Heteroleptic samarium(III) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy. Dalton Transactions, 47(31), pp. 10613-10625. (doi:10.1039/C8DT01452C) (PMID:29790545)

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Abstract

Addition of various oxidants to the near-linear Sm(II) complex [Sm(N††)2] (1), where N†† is the bulky bis(triisopropylsilyl)amide ligand {N(SiiPr3)2}, afforded a family of heteroleptic three-coordinate Sm(III) halide complexes, [Sm(N††)2(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N††)}3(μ2-I)3(μ3-I)2] (3), which formally contains one Sm(II) and two Sm(III) centres, was isolated during the synthesis of 2-I. Complexes 2-X are remarkably stable towards ligand redistribution, which is often a facile process for heteroleptic complexes of smaller monodentate ligands in lanthanide chemistry, including the related bis(trimethylsilyl)amide {N(SiMe3)2} (N′′). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα1 fluorescence-detected X-ray absorption spectrum recorded at the Sm L3-edge for 2-X exhibited a resolved pre-edge peak defined as an envelope quadrupole-allowed 2p → 4f transition. The X-ray absorption spectral features were successfully reproduced using time-dependent density functional theoretical (TD-DFT) calculations that synergistically supports the experimental observations as well as the theoretical model upon which the electronic structure and bonding in lanthanide complexes is derived.

Item Type:Articles
Additional Information:We thank the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C.A.P.G. and EP/K039547/1), The University of Manchester for a work experience bursary for J.G.C.K., and the University of Glasgow for funding. S.S. thanks the Scottish Funding Council for a Postgraduate and Early Career Researcher Exchange grant. K.M.L. thanks the National Science Foundation (CHE-1454455) and A. P. Sloan Foundation for financial support. We thank Dr Kenneth Finkelstein for technical assistance and Dr Pieter Glatzel (ESRF) for kindly providing Si(422) analyser crystals for use in the data collection. This work is based upon research conducted at the Cornell High Energy Synchrotron Source (CHESS), which is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-0936384, using the Macromolecular Diffraction at CHESS (MacCHESS) facility, which is supported by award GM-103485 from the National Institutes of Health, through its National Institute of General Medical Sciences.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen
Authors: Goodwin, C. A.P., Réant, B. L.L., Kragskow, J. G.C., DiMucci, I. M., Lancaster, K. M., Mills, D. P., and Sproules, S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN:1477-9226
ISSN (Online):1477-9234
Published Online:04 May 2018
Copyright Holders:Copyright © 2018 The Authors
First Published:First published in Dalton Transactions 47(31):10613-10625
Publisher Policy:Reproduced under a Creative Commons License

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