Design Strategies for Luminescent Titanocenes: Improving the Photoluminescence and Photostability of Arylethynyltitanocenes.

Complexes that undergo ligand-to-metal charge transfer (LMCT) to d metals are of interest as possible photocatalysts. CpTi(CPh) (where CPh = phenylethynyl) was reported to be weakly emissive in room-temperature (RT) fluid solution from its phenylethynyl-to-Ti LMCT state but readily photodecomposes. Coordination of CuX between the alkyne ligands to give CpTi(CPh)CuX (X = Cl, Br) has been shown to significantly increase the photostability, but such complexes are not emissive in RT solution.

Photochemistry and Photophysics of Charge-Transfer Excited States in Emissive / Heterobimetallic Titanocene Tweezer Complexes.

Transition-metal complexes that undergo ligand-to-metal charge transfer (LMCT) to metals are of interest as possible photocatalysts due to the lack of deactivating d-d states. Herein, the synthesis and characterization of nine titanocene complexes of the formula CpTi(CAr)·MX (where Ar = phenyl, dimethylaniline, or triphenylamine; and MX = CuCl, CuBr, or AgCl) are presented. Solid-state structural characterization demonstrates that MX coordinates to the alkyne tweezers and CuX coordination has a greater structural impact than AgCl.

Ligand-to-Metal Charge-Transfer Photophysics and Photochemistry of Emissive d Titanocenes: A Spectroscopic and Computational Investigation.

Complexes with ligand-to-metal charge-transfer (LMCT) excited states involving d metals represent a new design for photocatalysts. Herein, the photochemistry and photophysics of d titanocenes of the type CpTi(CR), where CR = ethynylphenyl (CPh), 4-ethynyldimethylaniline (CDMA), or 4-ethynyltriphenylamine (CTPA), have been investigated. CpTi(CPh) and CpTi(CDMA) have also been characterized by single-crystal X-ray diffraction.