A new series of three spin crossover (SCO) Fe(II) complexes based on a cyanocarbanion and on the neutral quinolin-8-amine (aqin) ligands, [Fe(aqin)2(tcnsme)2] (1), [Fe(aqin)2(tcnset)2] (2), and [Fe(aqin)2(tcnspr)2] (3), has been studied. The three complexes display similar molecular structures consisting of discrete [Fe(aqin)2(tcnsR)2] complexes [R = Me (1), Et (2), and Pr (3)]. Infrared spectroscopy and magnetic studies, performed on the three complexes, revealed the presence of similar SCO behaviors which strongly differ by their transition temperatures [234 K (1) < 266 K (2) < 360 K (3)]. The increase of the transition temperatures when passing from 1 to 3 may be explained by electronic and packing effects. Thus, when passing from Me (1) to Et (2) and Pr (3), the electron donor effect increases, resulting in an increase of the ligand field and, accordingly, in an increase of the transition temperature. On the other side, examination of the different coordination modes of the cyanocarbanions in the three complexes clearly reveals the crucial role of these coordination modes on the crystal packing and, therefore, on the transition temperature. We can, therefore, attribute the important increase of the transition temperature from complexes 1 to 3 to both effects: the electron donor character of the alkyl groups and the packing effects of the versatile cycnocarbanion ligands.
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14 April 2021
Research Article|
April 08 2021
Coordination isomerism in spin crossover (SCO) materials
Special Collection:
Spin Transition Materials: Molecular and Solid-State
Emmelyne Cuza;
Emmelyne Cuza
1
Univ Brest, CNRS, CEMCA
, 6 Avenue Le Gorgeu, C.S. 93837—29238 Brest Cedex 3, France
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Rachid Motei;
Rachid Motei
1
Univ Brest, CNRS, CEMCA
, 6 Avenue Le Gorgeu, C.S. 93837—29238 Brest Cedex 3, France
2
Laboratoire de Chimie Organique Appliquée, Faculté des Sciences Techniques de Fès, Université Sidi Mohammed Ben Abdellah
, Fès, Morocco
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Fatima Setifi;
Fatima Setifi
1
Univ Brest, CNRS, CEMCA
, 6 Avenue Le Gorgeu, C.S. 93837—29238 Brest Cedex 3, France
3
Laboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1
, Sétif 19000, Algeria
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Abdeslem Bentama;
Abdeslem Bentama
2
Laboratoire de Chimie Organique Appliquée, Faculté des Sciences Techniques de Fès, Université Sidi Mohammed Ben Abdellah
, Fès, Morocco
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Carlos J. Gómez-García
;
Carlos J. Gómez-García
4
Instituto de Ciencia Molecular (ICMol), Departamento de Química Inorgánica, Universidad de Valencia
, C/Catedrático José Beltrán 2, 46980 Paterna, Spain
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Smail Triki
Smail Triki
a)
1
Univ Brest, CNRS, CEMCA
, 6 Avenue Le Gorgeu, C.S. 93837—29238 Brest Cedex 3, France
a)Author to whom correspondence should be addressed: smail.triki@univ-brest.fr
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a)Author to whom correspondence should be addressed: smail.triki@univ-brest.fr
Note: This paper is part of the Special Topic on Spin Transition Materials: Molecular and Solid-State.
J. Appl. Phys. 129, 145501 (2021)
Article history
Received:
January 31 2021
Accepted:
March 18 2021
Citation
Emmelyne Cuza, Rachid Motei, Fatima Setifi, Abdeslem Bentama, Carlos J. Gómez-García, Smail Triki; Coordination isomerism in spin crossover (SCO) materials. J. Appl. Phys. 14 April 2021; 129 (14): 145501. https://doi.org/10.1063/5.0046055
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