Co-crystallization of the prominent Fe( ii ) spin-crossover (SCO) cation, [Fe(3-bpp) 2 ] 2+ (3-bpp = 2,6-bis(pyrazol-3-yl)pyridine), with a fractionally charged TCNQ δ − radical anion has afforded a hybrid complex [Fe(3-bpp) 2 ](TCNQ) 3 ·5MeCN (1·5MeCN, where δ = −0.67). The partially desolvated material shows semiconducting behavior, with the room temperature conductivity σ RT = 3.1 × 10 −3 S cm −1 , and weak modulation of conducting properties in the region of the spin transition. The complete desolvation, however, results in the loss of hysteretic behavior and a very gradual SCO that spans the temperature range of 200 K. A related complex with integer-charged TCNQ − anions, [Fe(3-bpp) 2 ](TCNQ) 2 ·3MeCN (2·3MeCN), readily loses the interstitial solvent to afford desolvated complex 2 that undergoes an abrupt and hysteretic spin transition centered at 106 K, with an 11 K thermal hysteresis. Complex 2 also exhibits a temperature-induced excited spin-state trapping (TIESST) effect, upon which a metastable high-spin state is trapped by flash-cooling from room temperature to 10 K. Heating above 85 K restores the ground-state low-spin configuration. An approach to improve the structural stability of such complexes is demonstrated by using a related ligand 2,6-bis(benzimidazol-2′-yl)pyridine (bzimpy) to obtain [Fe(bzimpy) 2 ](TCNQ) 6 ·2Me 2 CO (4) and [Fe(bzimpy) 2 ](TCNQ) 5 ·5MeCN (5), both of which exist as LS complexes up to 400 K and exhibit semiconducting behavior, with σ RT = 9.1 × 10 −2 S cm −1 and 1.8 × 10 −3 S cm −1 , respectively.
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Solvent-tunable exciton-charge transfer mixed state enhances emission of functionalized benzo[ rst ]pentaphene through symmetry breaking
A benzo[ rst ]pentaphene (BPP) substituted by two bis(methoxyphenyl)amino (MeOPA) groups (BPP–MeOPA) was synthesized and clearly characterized by NMR and single-crystal X-ray analysis. Detailed investigations of its photophysical properties, including transient absorption spectroscopy analyses, revealed that the introduction of the MeOPA groups breaks the symmetry of the BPP core, improving its absorption and emission from an S 1 state with both excitonic and charge-transfer character.
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- Award ID(s):
- 1719875
- PAR ID:
- 10411693
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 59
- Issue:
- 6
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 720 to 723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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