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Heterometallic Fe III /K Coordination Polymer with a Wide Thermal Hysteretic Spin Transition at Room Temperature
Author(s) -
Kang Soonchul,
Shiota Yoshihito,
Kariyazaki Akira,
Kanegawa Shinji,
Yoshizawa Kazunari,
Sato Osamu
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503392
Subject(s) - spin (aerodynamics) , polymer , thermal , thermal hysteresis , materials science , coordination polymer , crystallography , spin crossover , spin transition , condensed matter physics , chemistry , physics , thermodynamics , phase transition , composite material
The anionic Fe III complex exhibiting cooperative spin transition with a wide thermal hysteresis near room temperature, K[Fe(5‐Brthsa) 2 ] (5‐Brthsa‐H 2 =5‐bromosalicylaldehyde thiosemicarbazone), is reported. The hysteresis (Δ=69 K in the first cycle) shows a one‐step transition in heating mode and a two‐step transition in cooling mode. X‐ray structure analysis showed that the coexistence of hydrogen bond and cation–π interactions, as well as alkali metal coordination bonds, to give 2D coordination polymer structure. This result is contrary to previous reports of broad thermal hysteresis induced by coordination bonds of Fe II spin crossover coordination polymers (with 1D/3D structures), and by strong intermolecular interactions in the molecular packing through π–π stacking or hydrogen‐bond networks. As a consequence, the importance, or the very good suitability of alkali metal‐based coordination bonds and cation–π interactions for communicating cooperative interactions in spin‐crossover (SCO) compounds must be reconsidered.