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Dürrmann, Andreas ; Hörner, Gerald ; Weber, Birgit:
Remote H/F Tuning of Cooperativity in (NN'O)₂-Coordinate Iron(II) Complexes : Dynamic, Hysteretic, and Continuous Spin Crossover.
In: Crystal Growth & Design.
Bd. 23
(2023)
Heft 3
.
- S. 1743-1754.
ISSN 1528-7505
DOI: https://doi.org/10.1021/acs.cgd.2c01287
Abstract
Iron(II) complexes of meridional coordinating tridentate ligands have served as a very fruitful playground for spin crossover (SCO) research. In this work, we provide modular synthetic access to new meridional NN′O ligands derived from 8-aminoquinoline which vary the established Jäger-type planar N2O2 motif. Solid-state spin crossover properties of three homoleptic iron(II) complexes 1–3 with the general formula [Fe(Lx)2] (x denotes the remote substitution of the ligand: CH3/CH3 in HL1, CH3/CF3 in HL2, and CF3/CF3 in HL3) were probed via variable temperature single-crystal X-ray diffraction, SQUID magnetometry, and 57Fe Mössbauer spectroscopy. Subtle tuning of their substitution pattern at the outer sphere of the chelate ring translates into qualitatively different SCO profiles. The transition from dynamic SCO for 1 (TTIESST = 97 K; T1/2↑ = 124 K) to abrupt SCO with hysteresis for 2 (T1/2↓ = 132 K; T1/2↑ = 137 K) and continuous SCO for 3 (T1/2 = 280 K) indicates a successive loss of cooperativity, going parallel with the exchange of CH3 for CF3 groups. The decrease of cooperativity in SCO can be traced to ever-increasing steric bulk in the crystal, which reflects in locally varied interaction pattern, particularly in fully fluorinated 3. X-ray analysis revealed an isostructural lattice for 1 and 2 (monoclinic) but lower symmetry for 3 (triclinic) because of peculiarities in the crystal packing.
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| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Ehemalige ProfessorInnen > Professur Anorganische Chemie IV - Univ.-Prof. Dr. Birgit Weber Fakultäten Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie IV Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Ehemalige ProfessorInnen |
| Titel an der UBT entstanden: | Ja |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 27 Jan 2023 09:59 |
| Letzte Änderung: | 30 Aug 2023 12:25 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/73542 |