Complexes with ligand-to-metal charge-transfer (LMCT) excited states involving d⁰ metals represent a new design for photocatalysts. Herein, the photochemistry and photophysics of d⁰ titanocenes of the type Cp₂Ti(C₂R)₂, where C₂R = ethynylphenyl (C₂Ph), 4-ethynyldimethylaniline (C₂DMA), or 4-ethynyltriphenylamine (C₂TPA), have been investigated. Cp₂Ti(C₂Ph)₂ and Cp₂Ti(C₂DMA)₂ have also been characterized by single-crystal X-ray diffraction. The two aryl rings in Cp₂Ti(C₂DMA)₂ are nearly face-to-face in the solid state, whereas they are mutually perpendicular for Cp₂Ti(C₂Ph)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: Cp₂Ti(C₂Ph)₂, 575 nm and 0.65; Cp₂Ti(C₂TPA)₂, 642 nm and 0.42; Cp₂Ti(C₂DMA)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 ¹LMCT state. Whereas the spectroscopic data for Cp₂Ti(C₂TPA)₂ and Cp₂Ti(C₂DMA)₂ are well modeled using the optimized structure of these complexes, Cp₂Ti(C₂Ph)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 ³LMCT state. Optimization of the ³LMCT state demonstrates compression of the C–Ti–C bond angle, consistent with the known products of photodecomposition.

Ultrafast laser physics continues to advance at a rapid pace, driven primarily by the development of more powerful and sophisticated diode-pumping sources, the development of new laser materials, and new laser and amplification approaches such as optical parametric chirped-pulse amplification. The rapid development of high average power cryogenic laser sources seems likely to play a crucial role in realizing the long-sought goal of powerful ultrafast sources that offer concomitant high peak and average powers. In this paper, we review the optical, thermal, thermo-optic and laser parameters important to cryogenic laser technology, recently achieved laser and laser materials progress, the progression of cryogenic laser technology, discuss the importance of cryogenic laser technology in ultrafast laser science, and what advances are likely to be achieved in the near-future.