Correlations between ligand field Δo, spin crossover T1/2 and redox potential Epa in a family of five dinuclear helicates

A family of five new bis-bidentate azole–triazole Rat ligands (1,3-bis(5-(azole)-4-isobutyl-4H-1,2,4-triazol-3-yl)benzene), varying in choice of azole (2-imidazole, 4-imidazole, 1-methyl-4-imidazole, 4-oxazole and 4-thiazole), and the corresponding family of spin-crossover (SCO) and redox active triply bridged dinuclear helicates, [FeII2L3]4+, has been prepared and characterised. X-ray crystal structures show all five Fe(II) helicates are low spin at 100 K. Importantly, DOSY NMR confirms the intactness of these SCO-active dinuclear helicates in D3-MeCN solution, regardless of HS fraction: γHS(298 K) = 0–0.81. Variable temperature 1H NMR Evans and UV-vis studies reveal that the helicates are SCO-active in MeCN solution. Indeed, the choice of azole in the Rat ligand used in [Fe2L3]4+ tunes: (a) solution SCO T1/2 from 247 to 471 K, and (b) reversible redox potential, Em(FeII/III), from 0.25 to 0.67 V for four helicates, whilst one has an irreversible redox process, Epa = 0.78 V, vs. 0.01 M AgNO3/Ag. For the four reversible redox systems, a strong correlation (R2 = 0.99) is observed between T1/2 and Epa. Finally, the analogous Ni(II) helicates have been prepared to obtain Δo, establishing: (a) the ligand field strength order of the ligands: 4-imidazole (11 420) ∼ 1-methyl-4-imidazole (11 430) < 2-imidazole (11 505) ∼ 4-oxazole (11 516) < 4-thiazole (11 804 cm−1), (b) that Δo ([NiII2L3]4+) strongly correlates (R2 = 0.87) with T1/2 ([FeII2L3]4+), and (c) interestingly that Δo strongly correlates (R2 = 0.98) with Epa for the four helicates with reversible redox, so the stronger the ligand field strength, the harder it is to oxidise the Fe(II) to Fe(III).