Ligand-to-Metal Charge-Transfer Photophysics and Photochemistry of Emissive d 0 Titanocenes: A Spectroscopic and Computational Investigation

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Complexes with ligand-to-metal charge-transfer (LMCT) excited states involving d 0 metals represent a new design for photocatalysts. Herein, the photochemistry and photophysics of d 0 titanocenes of the type Cp 2 Ti(C 2 R) 2, where C 2 R = ethynylphenyl (C 2 Ph), 4-ethynyldimethylaniline (C 2 DMA), or 4-ethynyltriphenylamine (C 2 TPA), have been investigated. Cp 2 Ti(C 2 Ph) 2 and Cp 2 Ti(C 2 DMA) 2 have also been characterized by single-crystal X-ray diffraction. The two aryl rings in Cp 2 Ti(C 2 DMA) 2 are nearly face-to-face in the solid state, whereas they are mutually perpendicular for Cp 2 Ti(C 2 Ph) 2 . All three complexes are brightly emissive at 77 K but photodecompose at room temperature when irradiated into their lowest-energy absorption band. The emission wavelengths and photodecomposition quantum yields are as follows: Cp 2 Ti(C 2 Ph) 2, 575 nm and 0.65; Cp 2 Ti(C 2 TPA) 2, 642 nm and 0.42; Cp 2 Ti(C 2 DMA) 2, 672 nm and 0.25. Extensive benchmarking of the density functional theory (DFT) model against the structural data and of the time-dependent DFT (TDDFT) model against the absorption and emission data was performed using combinations of 13 different functionals and 4 basis sets. The model that predicted the absorption and emission data with the greatest fidelity utilized MN15/LANL2DZ for both the DFT optimization and the TDDFT. Computational analysis shows that absorption involves a transition to a 1 LMCT state. Whereas the spectroscopic data for Cp 2 Ti(C 2 TPA) 2 and Cp 2 Ti(C 2 DMA) 2 are well modeled using the optimized structure of these complexes, Cp 2 Ti(C 2 Ph) 2 required averaging of the spectra from multiple rotamers involving rotation of the Ph rings. Consistent with this finding, an energy scan of all rotamers showed a very flat energetic surface, with less than 1.3 kcal/mol separating the minimum and maximum. The computational data suggest that emission occurs from a 3 LMCT state. Optimization of the 3 LMCT state demonstrates compression of the C–Ti–C bond angle, consistent with the known products of photodecomposition.