Predictable Electronic Tuning By Choice of Azine Substituent in Five Iron(II) Triazoles: Redox Properties and DFT Calculations.

Abstract

Five new mononuclear iron(II) tris-ligand complexes, and four solvatomorphs, have been made from the azine-substituted 1,2,4-triazole ligands (Lazine ): [FeII (Lpyridazine )3 ](BF4 )2 (1), [FeII (Lpyrazine )3 ](BF4 )2 (2), [FeII (Lpyridine )3 ](BF4 )2 (3), [FeII (L2pyrimidine )3 ](BF4 )2 (4), and [FeII (L4pyrimidine )3 ](BF4 )2 (5). Single-crystal XRD and solid-state magnetometry reveal that all of them are low-spin (LS) iron(II), except for solvatomorph 5⋅4 H2 O. Evans method NMR studies in CD2 Cl2 , (CD3 )2 CO and CD3 CN show that all are LS in these solvents, except 5 in CD2 Cl2 (consistent with L4pyrimidine imposing the weakest field). Cyclic voltammetry in CH3 CN vs. Ag/0.01 m AgNO3 reveals an, at best quasi-reversible, FeIII/II redox process, with Epa increasing from 0.69 to 0.99 V as the azine changes: pyridine< pyridazine<2-pyrimidine<4-pyrimidine< pyrazine. The observed Epa values correlate linearly with the DFT calculated HOMO energies for the LS complexes.