Power of Three: Incremental Increase in the Ligand Field Strength of N‑Alkylated 2,2′-Biimidazoles Leads to Spin Crossover in Homoleptic Tris-Chelated Fe(II) Complexes
journal contributionposted on 18.04.2018 by Jeremy J. Hrudka, Hoa Phan, Jeff Lengyel, Andrey Yu. Rogachev, Michael Shatruk
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Homoleptic complexes [Fe(Ln)]X2 (L1 = 1,1′-(α,α′-o-xylyl)-2,2′-biimidazole, L2 = 1,1′-(α,α′-3,4-dibromo-o-xylyl)-2,2′-biimidazole, L3 = 1,1′-(α,α′-2,5-dimethoxy-o-xylyl)-2,2′-biimidazole; X = BF4– or ClO4–) were synthesized by direct reactions of the Fe(II) precursor salts and bidentate ligands L1, L2, or L3. All mononuclear complexes undergo gradual temperature-driven spin-crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states. Complexes with ligands L1 and L2 synthesized in methanol exhibit complete SCO with the midpoint of the LS↔HS conversion varying from 233 to 313 K, while complexes with ligand L3, crystallized from an ethanol/dichloromethane mixture, exhibit incomplete SCO with the residual HS/LS ratio of ∼1:4 for [Fe(L3)3](BF4)2 and ∼1:1 for [Fe(L3)3](ClO4)2. Complexes with L1 can also be recrystallized from ethanol/dichloromethane, in which case they exhibit very gradual and incomplete SCO, similar to those of the complexes with L3. The differences in magnetic behavior have been traced back to peculiarities of molecular packing observed in the corresponding crystal structures. Density-functional theoretical calculations provide justification to the SCO behavior of these complexes, as compared to the HS-only behavior observed for the parent [Fe(bim)3]2+ complex with nonalkylated 2,2′-biimidazole (bim).