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Attwood, M, Akutsu, H, Martin, L 
ORCID: https://orcid.org/0000-0002-5330-5700, Blundell, TJ ORCID: https://orcid.org/0000-0002-7296-1471, Le Maguere, P and Turner, SS,
2021.
Exceptionally high temperature spin crossover in amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complex revealed by variable temperature Raman spectroscopy and single crystal X-ray diffraction.
Dalton Transactions.
ISSN 1477-9226
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Abstract
The synthesis of a novel amide-functionalised 2,6-bis(pyrazol-1-yl)pyridine-4-carboxamide ligand (bppCONH2) is described. The complex salts [Fe(bppCONH2)2](BF4)2 and [Fe(bppCONH2)2](ClO4)2 were synthesised and characterised by SQUID magnetometry, differential scanning calorimetry, variable temperature Raman spectroscopy and single crystal X-ray diffraction. DSC measurements of [Fe(bppCONH2)2](BF4)2 indicate a spin-crossover (SCO) transition with T↑ at 481 K and T↓ at 461 K, showing a 20 K hysteresis. DSC for the perchlorate salt shows an SCO transition with T↑ at 459 K and T↓ at 445 K with a 14 K hysteresis. For the BF4− salt analysis of low and high-spin state crystal structures at 101, 290 and 500 K, suggest stabilisation of the low spin state due to the formation of 1D hydrogen-bonded cationic chains. Variable temperature Raman studies of the BF4 salt support the presence of a high temperature SCO. It is speculated that the presence of hysteresis may be attributed to differences in the inter-molecular hydrogen bonding in the low spin and high spin states.
| Item Type: | Journal article |
|---|---|
| Publication Title: | Dalton Transactions |
| Creators: | Attwood, M., Akutsu, H., Martin, L., Blundell, T.J., Le Maguere, P. and Turner, S.S. |
| Publisher: | Royal Society of Chemistry (RSC) |
| Date: | 2 August 2021 |
| ISSN: | 1477-9226 |
| Identifiers: | Number Type 10.1039/d1dt01743h DOI 1457035 Other |
| Rights: | This journal is © The Royal Society of Chemistry 2021. Open Access Article. Published on 02 August 2021. Downloaded on 8/16/2021 3:49:16 PM. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
| Divisions: | Schools > School of Science and Technology |
| Record created by: | Linda Sullivan |
| Date Added: | 17 Aug 2021 08:06 |
| Last Modified: | 17 Aug 2021 08:06 |
| URI: | https://irep.ntu.ac.uk/id/eprint/44004 |
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