Unprecedented bistability domain and interplay between spin crossover and polymorphism in a mononuclear iron(II) complex.
A mononuclear complex, [FeL2](BF4)2·xH2O (1LS∙xH2O), where L is 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine, can be converted into several phases showing different spin crossover regimes. In the first heating 1LS∙xH2O loses water molecules and converts into a mixture of two high spin phases, 1A/HS and 1C/HS. Further cycling produces the low spin phase 1A/LS. The transition 1A/LS↔1A/HS is accompanied by a 130 K wide hysteresis loop (Tc↑ = 490 K, Tc↓ = 360 K). Annealing the complex 1LS∙xH2O at 500 K yields a high spin phase 1C/HS. The phase 1C/HS undergoes spin conversion to the corresponding low spin phase 1C/LS on cooling, T1/2 ≈ 320 K. Dehydration of 1LS∙xH2O at 370 or 400 K yields a certain low spin phase, 1X/LS, which irreversibly transforms into a high spin phase 1B/HS, which, in turn, reversibly transforms to the low spin phase 1B/LS on cooling, T1/2 ≈ 320 K.
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia. bushuev@niic.nsc.ru mark.bushuev@gmail.com.
Mark B
MB
Bushuev
Vasiliy A
VA
Daletsky
Denis P
DP
Pishchur
Yuri V
YV
Gatilov
Ilya V
IV
Korolkov
Elena B
EB
Nikolaenkova
Viktor P
VP
Krivopalov