Spin Crossover in Fe(II) Complexes with N4S2 Coordination.
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.
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Alejandra
A
Arroyave
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , Campusvej 55, 5230 Odense M, Denmark.
Anders
A
Lennartson
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Alina
A
Dragulescu-Andrasi
Department of Chemistry, University of Copenhagen , Universitetsparken 5, Copenhagen, Denmark.
Kasper S
KS
Pedersen
Department of Chemistry, University of Copenhagen , Universitetsparken 5, Copenhagen, Denmark.
Stergios
S
Piligkos
National High Magnetic Field Laboratory , 1800 East Paul Dirac Drive, Tallahassee, Florida 32310, United States.
Sebastian A
SA
Stoian
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.|National High Magnetic Field Laboratory , 1800 East Paul Dirac Drive, Tallahassee, Florida 32310, United States.
Samuel M
SM
Greer
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Chongin
C
Pak
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Oleksandr
O
Hietsoi
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Hoa
H
Phan
National High Magnetic Field Laboratory , 1800 East Paul Dirac Drive, Tallahassee, Florida 32310, United States.|Department of Physics, Florida State University , 315 Keen Building, Tallahassee, Florida 32306, United States.
Stephen
S
Hill
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark , Campusvej 55, 5230 Odense M, Denmark.
Christine J
CJ
McKenzie
Department of Chemistry and Biochemistry, Florida State University , 95 Chieftan Way, Tallahassee, Florida 32306, United States.
Michael
M
Shatruk