The metal-to-ligand-charge-transfer (MLCT) excited state of Cu(I) diimine complexes is known to undergo structural reorganization, transforming from a pseudotetrahedral D(2d) symmetry in the ground state to a flattened D(2) symmetry in the MLCT state, which allows ligation with a solvent molecule, forming an exciplex intermediate. Therefore, the structural factors that influence the coordination geometry change and the solvent accessibility to the copper center in the MLCT state could be used to control the excited state properties. In this study, we investigated an extreme case of the steric hindrance caused by attaching bulky tert-butyl groups in bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I), [Cu(I)(dtbp)(2)](+). The two bulky tert-butyl groups on the dtbp ligand lock the MLCT state into the pseudotetrahedral coordination geometry and completely block the solvent access to the copper center in the MLCT state of [Cu(I)(dtbp)(2)](+). Using ultrafast transient absorption spectroscopy and time-resolved emission spectroscopy, we investigated the MLCT state property changes due to the steric hindrance and demonstrated that [Cu(I)(dtbp)(2)](+) exhibited a long-lived emission but no subpicosecond component that was previously assigned as the flattening of the pseudotetrahedral coordination geometry. This suggests the retention of its pseudotetrahedral D(2d) symmetry and the blockage of the solvent accessibility. We made a comparison between the excited state dynamics of [Cu(I)(dtbp)(2)](+) with its mono-tert-butyl counterpart, bis(2-tert-butyl-1,10-phenanthroline)copper(I) [Cu(I)(tbp)(2)](+). The subpicosecond component assigned to the flattening of the D(2d) coordination geometry in the MLCT excited state was again present in the latter because the absence of a tert-butyl on the phenanthroline allows flattening to the pseudotetrahedral coordination geometry. Unlike the [Cu(I)(dtbp)(2)](+), [Cu(I)(tbp)(2)](+) exhibited no detectable emission at room temperature in solution. These results provide new insights into the manipulation of various excited state properties in Cu diimine complexes by certain key structural factors, enabling optimization of these systems for solar energy conversion applications.

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The effects of structural constraints on the metal-to-ligand charge transfer (MLCT) excited state structural dynamics of cuprous bis-2,9-diphenyl-phenanthroline ([Cu(I)(dpp)(2)](+)) in both coordinating acetonitrile and noncoordinating toluene were studied using X-ray transient absorption (XTA) spectroscopy and density functional theory (DFT) calculations. The phenyl groups attached to the phenanthroline ligands not only effectively shield the Cu(I) center from solvent molecules, but also force a flattened tetrahedral coordination geometry of the Cu(I) center. Consequently, the MLCT state lifetime in [Cu(I)(dpp)(2)](+) is solvent-independent, unlike the previously studied 2,9-methyl substituted bis-phenanthroline Cu(I) complex. The MLCT state of [Cu(I)(dpp)(2)](+) still undergoes a "pseudo Jahn-Teller distortion," with the angle between the two phenanthroline ligand planes decreased further by 7°. The XTA results indicate that, in the MLCT excited state of [Cu(I)(dpp)(2)](+), the phenyls at the 2, 9 positions of the phenanthroline rotate, breaking the π-π interaction with the phenanthroline ligands without ever rotating in-plane with the phenanthroline ligands. Hence, the transferred electron density from the Cu(I) center is localized on the phenanthroline moiety with no charge density present on the phenyl rings. The insight about the effect of the structural constraints on the MLCT state properties will guide the design of Cu(I) diimine complexes with suitable excited-state properties to function as earth-abundant dye sensitizers for solar electricity generation.

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