- Award ID(s):
- 1664998
- NSF-PAR ID:
- 10279892
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry A
- Volume:
- 124
- Issue:
- 42
- ISSN:
- 1089-5639
- Page Range / eLocation ID:
- 8744 to 8752
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Co‐crystallization of the spin‐crossover (SCO) cationic complex, [Fe(1‐bpp)2]2+(1‐bpp=2,6‐bis(pyrazol‐1‐yl)pyridine) with fractionally charged organic anion TCNQδ−(0<δ<1) afforded hybrid materials [Fe(1‐bpp)2](TCNQ)3.5 ⋅ 3.5MeCN (
1 ) and [Fe(1‐bpp)2](TCNQ)4 ⋅ 4DCE (2 ), where TCNQ=7,7,8,8‐tetracyanoquinodimethane, MeCN=acetonitrile, and DCE=1,2‐dichloroethane. Both materials exhibit semiconducting behavior, with the room‐temperature conductivity values of 1.1×10−4 S/cm and 1.7×10−3 S/cm, respectively. The magnetic behavior of both complexes exhibits strong dependence on the content of the interstitial solvent. Complex1 undergoes a gradual temperature‐driven SCO, with the midpoint temperature ofT 1/2=234 K. The partial solvent loss by1 leads to the increase in theT 1/2value while complete desolvation renders the material high‐spin (HS) in the entire studied temperature range. In the case of2 , the solvated complex shows a gradual SCO withT 1/2=166 K only when covered with a mother liquid, while the facile loss of interstitial solvent, even at room temperature, leads to the HS‐only behavior.