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Remote H/F Tuning of Cooperativity in (NN′O)2-Coordinate Iron(II) Complexes: Dynamic, Hysteretic, and Continuous Spin Crossover

Cite this: Cryst. Growth Des. 2023, 23, 3, 1743–1754
Publication Date (Web):January 26, 2023
https://doi.org/10.1021/acs.cgd.2c01287
Copyright © 2023 The Authors. Published by American Chemical Society

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    Abstract

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    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 13 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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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.2c01287.

    • Furthermore, data can be provided from the authors upon reasonable request; the SI contains crystallographic details; illustrations of asymmetric units; snapshots of crystals and bulk material; metrical data of intermolecular interactions; powder X-ray diffractograms; 57Fe Mössbauer spectrum of quench-cooled 1; 1H NMR spectra of the ligands (PDF)

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    CCDC 22155132215520 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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