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Solvent-Induced Polymorphism of Iron(II) Spin Crossover Complexes

Salitros, Ivan; Fuhr, Olaf; Ruben, Mario

Abstract:
Two new mononuclear iron(II) compounds (1) and (2) of the general formula [Fe(L) $_{2}$](BF$_{4}$)$_{2}$·nCH$_{3}$CN (L = 4-(2-bromoethyn-1-yl)-2,6-bis(pyrazol-1-yl)pyridine, n = 1 for (1) and n = 2 for compound (2)), were synthesized. The room temperature crystallization afforded concomitant formation of two different solvent analogues: compound (1) exhibiting triclinic P-1 and compound (2) monoclinic C2/c symmetry. Single-crystal X-ray studies confirmed the presence of the LS (low-spin) state for both compounds at 180 K and of the HS (high-spin) state for compound (2) at 293 K, in full agreement with the magnetic investigations for both solvent polymorphs. Compound (1) exhibits spin transition above 293 K followed by subsequent solvent liberation, while the spin transition of (2) takes already place at 237 K. After complete solvent removal from the crystal lattice, compound (1d) (the desolvated polymorph derived from (1)) exhibits spin transition centered at 342 K accompanied by a thermal hysteresis loop, while the analogous compound (2d) (the desolvated derivate of compound (2)) remains blocked in the HS state over all the invest ... mehr


Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Karlsruhe Nano Micro Facility (KNMF)
Publikationstyp Zeitschriftenaufsatz
Jahr 2016
Sprache Englisch
Identifikator DOI: 10.3390/ma9070585
ISSN: 1996-1944
URN: urn:nbn:de:swb:90-600387
KITopen ID: 1000060038
HGF-Programm 43.21.04; LK 01
Erschienen in Materials
Band 9
Heft 7
Seiten Art.Nr.:506
Lizenz CC BY 4.0: Creative Commons Namensnennung 4.0 International
Schlagworte spin crossover, iron(II) complexes, molecular magnetism, polymorphism
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