posted on 2016-06-09, 18:23authored byAlejandra Arroyave, Anders Lennartson, Alina Dragulescu-Andrasi, Kasper S. Pedersen, Stergios Piligkos, Sebastian A. Stoian, Samuel M. Greer, Chongin Pak, Oleksandr Hietsoi, Hoa Phan, Stephen Hill, Christine J. McKenzie, Michael Shatruk
Reactions
of Fe(II) precursors with the tetradentate ligand S,S′-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate
NCE– coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover
(SCO). As the ligand field strength increases from NCS– to NCSe– to NCBH3–, the SCO shifts to higher temperatures. Complex 1 exhibits
only a partial (15%) conversion from the high-spin (HS) to the low-spin
(LS) state, with an onset around 100 K. Complex 3 exhibits
a complete SCO with T1/2 = 243 K. While
the γ-2 polymorph also shows the complete SCO with T1/2 = 192 K, the α-2 polymorph
exhibits a two-step SCO with the first step leading to a 50% HS →
LS conversion with T1/2 = 120 K and the
second step proceeding incompletely in the 80–50 K range. The
amount of residual HS fraction of α-2 that remains
below 60 K depends on the cooling rate. Fast flash-cooling allows
trapping of as much as 45% of the HS fraction, while slow cooling
leads to a 14% residual HS fraction. The slowly cooled sample of α-2 was subjected to irradiation in the magnetometer cavity
resulting in a light-induced excited spin state trapping (LIESST)
effect. As demonstrated by Mössbauer spectroscopy, an HS fraction
of up to 85% could be achieved by irradiation at 4.2 K.