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Subtlety of the spin-crossover phenomenon observed with dipyridylamino-substituted triazine ligands

AuthorsWannarit, Nanthawat; Roubeau, Olivier; Youngme, Sujittra; Gamez, Patrick
Issue Date2013
CitationEuropean Journal of Inorganic Chemistry (5-6): 730-737 (2013)
AbstractReactions of the new, closely related ligands 4,6-dichloro-N,N-di(pyridine-2-yl)-1,3,5-triazine-amine (Cldpat) and 6-chloro-N′-phenyl-N,N-di(pyridin-2-yl)-1,3,5-triazine-2,4-diamine (Cladpat) with iron(II) thiocyanate produced coordination compounds with drastically distinct magnetic properties. The compound trans-[Fe(Cldpat)2(NCS)2](H2O) (1) is a high-spin complex from room temperature down to 5 K whereas the analogous compound trans-[Fe(Cladpat)2(NCS)2] (2) exhibits spin-crossover (SCO) properties with T1/2 = 178 K. Compounds 1 and 2 (both in its low-spin and high-spin states) have been structurally characterized by X-ray diffraction studies, which revealed identical metal coordination spheres. The SCO properties of 2 have been thoroughly investigated by temperature-dependent magnetic susceptibility measurements and differential scanning calorimetry (DSC), and a LIESST process with rapid relaxation of the trapped HS species has been observed. The equivalent coordination compound with selenocyanate anions, namely [Fe(Cladpat)2(NCSe)2] (3) also displays SCO properties, although more gradual and with a lower T1/2 value of 166 K.
Publisher version (URL)http://dx.doi.org/10.1002/ejic.201201085
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