Magri, Giuseppina, Folli, Andrea  ORCID: https://orcid.org/0000-0001-8913-6606 and Murphy, Damien M. ORCID: https://orcid.org/0000-0002-5941-4879
2022.
Monitoring the substrate-induced spin-state distribution in a Cobalt(II)-Salen complex by EPR and DFT.
European Journal of Inorganic Chemistry
2022
(9)
, e202101071.
10.1002/ejic.202101071
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Abstract
Ground state changes of (R,R’)-N,N’-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II), following coordination of various pyridyl substrate has been examined by CW EPR, pulsed relaxation measurements and DFT. The solution-based Co(II) complex possesses a low spin (LS) state urn:x-wiley:14341948:media:ejic202101071:ejic202101071-math-0001 (with g-values of 1.96, 1.895, 3.14). Upon coordination of the pyridyl substrate, the resulting bound adduct reveals a distribution of LS ‘base-on’ species, possessing a urn:x-wiley:14341948:media:ejic202101071:ejic202101071-math-0002 electronic ground state (with g-values of 2.008, 2.2145, 2.46) and a high spin (HS) species (with geff = 4.6). DFT indicated that the energy gap between the LS and HS state is dramatically lowered (ΔE < 25 kJmol−1) following substrate coordination. DFT suggests the main geometrical difference between the LS and HS systems is the severe puckering of the N2O2 ligand backbone. The results revealed a tentative dependency on the pKa−H of the substrates for the spin distribution where, in most cases, the higher pKa−H substrate values favoured the HS species.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Additional Information: | This is an open access article under the terms of the Creative Commons Attribution License |
| Publisher: | Wiley-VCH Verlag |
| ISSN: | 1434-1948 |
| Funders: | EPSRC |
| Date of First Compliant Deposit: | 9 March 2022 |
| Date of Acceptance: | 11 February 2022 |
| Last Modified: | 06 Jan 2024 04:24 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/148200 |
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