Photo-switchable spin-crossover iron(III) compound based on intermolecular interactions

• Published in: Journal of Inclusion Phenomena and Macrocyclic Chemistry Vol. 71; no. 3-4; pp. 363 - 369
• Main Authors: Shimizu, Tetsuya, Komatsu, Yasuka, Kamihata, Hidenobu, Lee, Young Hoon, Fuyuhiro, Akira, Iijima, Seiichiro, Hayami, Shinya
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Netherlands 01.12.2011
• Subjects: Chemistry; Chemistry and Materials Science; Crystallography and Scattering Methods; Food Science; Organic Chemistry; Original Article; Intermolecular interaction; Iron(III); LIESST; Spin-crossover
• ISSN: 0923-0750; 1573-1111
• DOI: 10.1007/s10847-011-9960-3

Iron(III) spin-crossover compounds, [Fe(qnal) 2 ]CF 3 SO 3 ·MeOH (1·MeOH) and [Fe(qnal) 2 ]CF 3 SO 3 ·acetone (1·acetone) were prepared and their spin transition properties were characterized by magnetic susceptibility measurement, Mössbauer spectroscopy and single crystal analysis. Two iron(III) compounds exhibited abrupt spin transition with thermal hysteresis loop ( T 1/2 ↑ = 115 K and T 1/2 ↓ = 104 K for 1·MeOH, and T 1/2 ↑ = 133 K and T 1/2 ↓ = 130 K for 1·acetone). Single crystal analysis revealed both of the structures in high-spin (HS) and low-spin (LS) states for 1·acetone. The difference of bond length between the HS and LS states for 1·acetone was ~0.10 Å, which was corresponding to that of typical iron(III) SCO compounds. Specially, it showed strong intermolecular interactions by π – π stacking formed between the neighbor complexes leading to 2-D sheet. Both 1·MeOH and 1·acetone exhibited LIESST effect when it was illuminated at 1000 nm. We also confirmed that the introduction of strong intermolecular interactions, such as π – π stacking, can play an important role in LIESST effect.