TY - JOUR
T1 - Mechanism of reversible spin transition with a thermal hysteresis loop in [FeIII(qsal)2][Ni(dmise)2] · 2CH3CN
T2 - Selenium analogue of the precursor of an Fe(III) spin-crossover molecular conducting system
AU - Takahashi, Kazuyuki
AU - Mori, Hatsumi
AU - Kobayashi, Hayao
AU - Sato, Osamu
N1 - Funding Information:
K.T. is grateful to Ms. Y. Isono for her experimental support and to Mr. Y. Okano for the use of his programs of molecular orbital calculations in this work. This work was partly supported by a Grant-in-Aid for Scientific Research on the Priority Area of Molecular Conductors (No. 18028024) and a Grant-in-Aid for Young Scientists (B) (No. 19750107) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.
PY - 2009/6/22
Y1 - 2009/6/22
N2 - A novel Fe(III) spin-crossover complex, [Fe(qsal)2][Ni(dmise)2] · 2CH3CN 1 [qsalH = N-(8-quinolyl)-salicylaldimine, dmise = 4,5-dithiolato-1,3-dithiole-2-selone] was prepared. The magnetic susceptibility measurements revealed 1 exhibited a cooperative spin transition with a thermal hysteresis loop of 15 K. The high and the low temperature structures of 1 indicated three-dimensional intermolecular π-π interactions play a key role in the cooperative spin transition, accompanying a reversible molecular slipping of π-dimer of Ni(dmise)2 along the molecular long axis. The transfer integral calculation for 1 suggested the π-dimer of Ni(dmise)2 is in the spin singlet state.
AB - A novel Fe(III) spin-crossover complex, [Fe(qsal)2][Ni(dmise)2] · 2CH3CN 1 [qsalH = N-(8-quinolyl)-salicylaldimine, dmise = 4,5-dithiolato-1,3-dithiole-2-selone] was prepared. The magnetic susceptibility measurements revealed 1 exhibited a cooperative spin transition with a thermal hysteresis loop of 15 K. The high and the low temperature structures of 1 indicated three-dimensional intermolecular π-π interactions play a key role in the cooperative spin transition, accompanying a reversible molecular slipping of π-dimer of Ni(dmise)2 along the molecular long axis. The transfer integral calculation for 1 suggested the π-dimer of Ni(dmise)2 is in the spin singlet state.
UR - http://www.scopus.com/inward/record.url?scp=67349235599&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=67349235599&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2008.11.047
DO - 10.1016/j.poly.2008.11.047
M3 - Article
AN - SCOPUS:67349235599
SN - 0277-5387
VL - 28
SP - 1776
EP - 1781
JO - Polyhedron
JF - Polyhedron
IS - 9-10
ER -