| Autor: |
Dunlop D; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic.; Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Praha 2, Czech Republic., Večeřa M; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Gyepes R; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic.; Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Praha 2, Czech Republic., Kubát P; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Lang K; Institute of Inorganic Chemistry of the Czech Academy of Sciences, 250 68 Husinec-Řež, Czech Republic., Horáček M; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Pinkas J; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Šimková L; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Liška A; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic., Lamač M; J. Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences, Dolejškova 2155/3, 182 23 Praha 8, Czech Republic. |
| Abstrakt: |
Cationic group 4 metallocene complexes with pendant imine and pyridine donor groups were prepared as stable crystalline [B(C 6 F 5 ) 4 ] - salts either by protonation of the intramolecularly bound ketimide moiety in neutral complexes [(η 5 -C 5 Me 5 ){η 5 -C 5 H 4 CMe 2 CMe 2 C(R)═N-κ N }MCl] (M = Ti, Zr, Hf; R = t -Bu, Ph) by PhNMe 2 H + [B(C 6 F 5 ) 4 ] - to give [(η 5 -C 5 Me 5 ){η 5 -C 5 H 4 CMe 2 CMe 2 C(R)═NH-κ N }MCl] + [B(C 6 F 5 ) 4 ] - or by chloride ligand abstraction from the complexes [(η 5 -C 5 Me 5 )(η 5 -C 5 H 4 CMe 2 CH 2 C 5 H 4 N)MCl 2 ] (M = Ti, Zr) by Li[B(C 6 F 5 ) 4 ]·2.5Et 2 O to give [(η 5 -C 5 Me 5 )(η 5 -C 5 H 4 CMe 2 CH 2 C 5 H 4 N-κ N )MCl] + [B(C 6 F 5 ) 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 ( 3 LMCT) 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. |
