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Title: Competition between Solvent···Solvent and Solvent···Solute Interactions in the Microhydration of the Tetrafluoroborate Anion, BF 4 – (H 2 O) n=1,2,3,4
Award ID(s):
1757888 2154403
NSF-PAR ID:
10471659
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
ACS
Date Published:
Journal Name:
The Journal of Physical Chemistry A
Volume:
127
Issue:
42
ISSN:
1089-5639
Page Range / eLocation ID:
8806 to 8820
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. null (Ed.)
  2. 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. Complex1undergoes a gradual temperature‐driven SCO, with the midpoint temperature ofT1/2=234 K. The partial solvent loss by1leads to the increase in theT1/2value 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 withT1/2=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.

     
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