Predictable Substituent Control of Co^III/II Redox Potential and Spin Crossover in Bis(dipyridylpyrrolide)cobalt...

A family of five easily prepared tridentate monoanionic 2,5-dipyridyl-3-(R¹)-4-(R²)-pyrrolide anions (dpp^R1,R2)^-, varying in the nature of the R¹ and R² substituents [R¹, R² = CN, Ph; CO₂Et, CO₂Et; CO₂Me, 4-Py; CO₂Me, Me; Me, Me], has been used to generate the analogous family of neutral [Co^II(dpp^R1,R2)₂] complexes, two of which are structurally characterized at both 100 and 298 K. Both the oxidation and spin states of these complexes can be switched in response to appropriate external stimuli. All complexes, except [Co^II(dpp^Me,Me)₂], exhibit gradual spin crossover (SCO) in the solid state, and SCO activity is observed for three complexes in CDCl₃ solution. The cobalt(II) centers in the low spin (LS) complexes are Jahn-Teller tetragonally compressed along the pyrrolide-Co-pyrrolide axis. The complexes in their high spin (HS) states are more distorted than in the LS states, as is also usually the case for SCO active iron(II) complexes. The reversible Co^III/II redox potentials are predictably tuned by choice of substituents R¹ and R², from -0.95 (Me,Me) to -0.45 (CN,Ph) V vs Fc⁺/Fc, with a linear correlation observed between E_1/2(Co^III/II) and the Swain-Lupton parameters of the pyrrolide substituents.