Luminescent Cationic Group 4 Metallocene Complexes Stabilized by Pendant N-Donor Groups

Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C₆F₅)₄]^- salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η⁵-C₅Me₅){η⁵-C₅H₄CMe₂CMe₂C(R)═N-κN}MCl] (M = Ti, Zr, Hf; R = t-Bu, Ph) by PhNMe₂H⁺[B(C₆F₅)₄]^- to give [(η⁵-C₅Me₅){η⁵-C₅H₄CMe₂CMe₂C(R)═NH-κN}MCl]⁺[B(C₆F₅)₄]^- or by chloride ligand abstraction from the complexes [(η⁵-C₅Me₅)(η⁵-C₅H₄CMe₂CH₂C₅H₄N)MCl₂] (M = Ti, Zr) by Li[B(C₆F₅)₄]·2.5Et₂O to give [(η⁵-C₅Me₅)(η⁵-C₅H₄CMe₂CH₂C₅H₄N-κN)MCl]⁺[B(C₆F₅)₄]^-. Solid state structures of the new compounds were established by X-ray diffraction analysis, and their electrochemical behavior was studied by cyclic voltammetry. The cationic complexes of Zr and Hf, compared to the corresponding neutral species, exhibited significantly enhanced luminescence predominantly from triplet ligand-to-metal (³LMCT) excited states with lifetimes up to 62 μs and quantum yields up to 58% in the solid state. DFT calculations were performed to explain the structural features and optical and electrochemical properties of the complexes.