2024-03-28T14:18:52Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1817442019-05-21T00:58:05Zcom_10261_31com_10261_3col_10261_284
Bartual-Murgui, Carlos
Vela, Sergi
Darawsheh, Mohanad
Diego, Rosa
Teat, Simon J.
Roubeau, Olivier
AromÃ, Guillem
2019-05-20T10:28:23Z
2019-05-20T10:28:23Z
2017
Inorganic Chemistry Frontiers 4(8): 1374-1383 (2017)
http://hdl.handle.net/10261/181744
10.1039/C7QI00347A
2052-1553
http://dx.doi.org/10.13039/501100003741
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100001665
http://dx.doi.org/10.13039/100000015
http://dx.doi.org/10.13039/501100002809
http://dx.doi.org/10.13039/501100000781
http://dx.doi.org/10.13039/501100003329
Identifying and quantifying the individual factors affecting the temperature and properties of the spin crossover in transition metal complexes is a challenging task, because many variables are involved. While the most decisive factor is the crystal field imparted by ligands around the active metal center, some less common actors are intramolecular steric repulsions or non-covalent interactions. A series of three Fe(II) complexes of 1,3bpp derivatives of (2-(pyrazol-1-yl)-6-(1H-pyrazol-3-yl)pyridine) have been prepared and characterized crystallographically to probe these effects: [Fe(1,3bpp)2](ClO4)2 (1), [Fe(met1,3bpp)2](ClO4)2 (2) and [Fe(dimet1,3bpp)2](ClO4)2 (3). The ligands exhibit none, one or two methyl substituents on the pyrazol-1-yl heterocycle. These groups exert a dramatic effect on the SCO temperature in the solid state, and, most significantly, in solution (with TSCO (3) > TSCO (1) > TSCO (2)). Extensive DFT calculations have unveiled the origin of these effects which lie in the intramolecular non-covalent or steric interactions rather than resulting from crystal field effects.
eng
http://creativecommons.org/licenses/by/3.0/
openAccess
A probe of steric ligand substituent effects on the spin crossover of Fe(II) complexes
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