Capel Berdiell, I orcid.org/0000-0003-3828-7097, García-López, V orcid.org/0000-0001-7090-6041, Howard, MJ orcid.org/0000-0002-0762-2887 et al. (2 more authors) (2021) The Effect of Tether Groups on the Spin States of Iron(II)/Bis[2,6-Di(pyrazol-1-yl)pyridine] Complexes. Dalton Transactions: an international journal of inorganic chemistry. ISSN 1477-9226
Abstract
The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(II) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 whose complex remains predominantly high-spin. Crystalline [Fe(L6)2][ClO4]2·2MeCN contains three unique cation sites which alternate within hydrogen-bonded chains, and undergo gradual SCO at different temperatures upon warming. The SCO midpoint temperature (T½) of the complexes in CD3CN solution ranges between 208-274 K, depending on the functional group linking the tether groups to the pyridyl ring. This could be useful for predicting how these complexes might behave when deposited on gold or silica surfaces.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © Royal Society of Chemistry 2021. This is an author produced version of an article accepted for publication in Dalton Transactions. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Funding Information: | Funder Grant number Leverhulme Trust RPG-2015-095 |
Depositing User: | Symplectic Publications |
Date Deposited: | 06 May 2021 08:13 |
Last Modified: | 08 Jan 2025 15:03 |
Status: | Published online |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/D1DT01076J |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:173715 |