Enantioselective Guest Effect on the Spin State of a Chiral Coordination Framework

• Published in: Chemistry : a European journal Vol. 21; no. 50; pp. 18076 - 18079
• Main Authors: Gural'skiy, Il'ya A., Kucheriv, Olesia I., Shylin, Sergii I., Ksenofontov, Vadim, Polunin, Ruslan A., Fritsky, Igor O.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 07.12.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Chemistry; Chirality; coordination frameworks; Crossovers; guest effect; Inclusions; Inorganic compounds; Mossbauer spectroscopy; spin crossover; Spin transition; stereoselectivity; Switches; Transition temperature; coordination frameworks; chirality; guest effect; stereoselectivity; spin crossover
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201503365

The diversity of spin crossover (SCO) complexes that, on the one hand, display variable temperature, abruptness and hysteresis of the spin transition, and on the other hand, are spin‐sensitive to the various guest molecules, makes these materials unique for the detection of different organic and inorganic compounds. We have developed a homochiral SCO coordination polymer with a spin transition sensitive to the inclusion of the guest 2‐butanol, and these solvates with (R)‐ and (S)‐alcohols demonstrate different SCO behaviours depending on the chirality of the organic analyte. A stereoselective response to the guest inclusion is detected as a shift in the temperature of the transition both from dia‐ to para‐ and from para‐ to diamagnetic states in heating and cooling modes respectively. Furthermore, the Mössbauer spectroscopy directly visualizes how the metallic centres in a chiral coordination framework differently sense the interaction with guests of different chiralities. Stereoselective switch: Spin crossover in a homochiral coordinatiom polymer is sensitive to the inclusion of the guest 2‐butanol, and solvates with (R)‐ and (S)‐alcohols demonstrate different transition behaviours depending on the chirality of the organic analyte. A stereoselective response to the guest inclusion is detected as a shift of transition temperatures and in Mössbauer experiments (see figure; LS=low spin, HS=high spin).