2D Bimetallic Oxalate‐Based Ferromagnets with Inserted [Fe(4‐Br‐sal2‐trien)]+ and [Fe(3‐R‐sal2‐trien)]+ (R = Br, Cl and CH3O) FeIII Spin‐Crossover Complexes. Issue 5 (19th December 2012)

• Record Type: Journal Article
• Authors: Clemente‐León, Miguel; Coronado, Eugenio; López‐Jordà, Maurici
• Other Names: Murray Keith S. sponsoringEditor.; Oshio Hiroki sponsoringEditor.; Real Jose Antonio sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 5/6(2013)
• Page Start: 753
• Page End: 762
• Publication Date: 2012-12-19
• Subjects: Spin crossover -- Magnetic properties -- Oxalate complexes -- Coordination chemistry -- Schiff bases; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201201113
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The syntheses, structures and magnetic properties of the compounds of formula [Fe III (4‐Br‐sal2 ‐trien)][Mn II Cr III (ox)3 ]0.67 Cl0.33 · CH3 OH_solvate (1 ), [Fe III (3‐Br‐sal2 ‐trien)][Mn II Cr III (ox)3 ]· (CH3 CN)2 (2 ), [Fe III (3‐Cl‐sal2 ‐trien)][Mn II Cr III (ox)3 ]· (CH3 OH)2 · (CH3 CN)2 (3 ) and [Fe III (3‐CH3 O‐sal2 ‐trien)][Mn II Cr III (ox)3 ]· (CH3 OH)· (H2 O)1.5 · (CH2 Cl2 )0.5 (4 ) are reported. The four structures present a 2D honeycomb anionic layer formed by Mn II and Cr III ions linked through oxalate ligands and a cationic layer of the Fe III complexes intercalated between the 2D oxalate network. The main differences compared with previous 2D oxalate‐based structures are the presence of double layers of cations in compounds1, 3 and4 and porous channels in the structures of1 and4 filled with disordered solvent molecules. The magnetic properties indicate that the inserted Fe III cations undergo an almost complete spin crossover above 300 K in1 and a partial spin crossover in3 and4 that coexists with a ferromagnetic ordering of the oxalate network. In the case of2, the inserted cation remains in the HS from 2 to 300 K. Therefore, 1, 3 and4 are multifunctional compounds with coexistence of spin crossover and magnetic ordering. Conversely, photomagnetic characterization shows that1 and3 do not present a LIESST effect in contrast to the 2D compound [Fe III (sal2 ‐trien)][Mn II Cr III (ox)3 ]· (CH2 Cl2 ). These results could help to clarify this rare property for a Fe III complex. Abstract : The syntheses, structures and magnetic properties of four compounds formed by insertion of [Fe(4‐Br‐sal2 ‐trien)] + (1 ) and [Fe(3‐R‐sal2 ‐trien)] + [R = Br (2 ), Cl (3 ) and CH3 O (4 )] Fe III spin‐crossover complexes into a 2D honeycomb anionic layer formed by Mn II and Cr III ions linked through oxalate ligands are reported in this paper. The four compounds behave as ferromagnets with a T c around 5 K.