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Real-time observation of the photoinduced structural change of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) by femtosecond fluorescence spectroscopy: a realistic potential curve of the Jahn-Teller distortion.

In copper(I) complex [Cu(dmphen)(2)]+ (dmphen = 2,9-dimethyl-1,10-phenanthroline), a "flattening" structural change is induced with 1MLCT excitation, which is a prototype of the structural change accompanied with Cu(I)/Cu(II) conversion in copper complexes. Femtosecond and picosecond emission dynamics of this complex were investigated in solution at room temperature with optically allowed S(2) <-- S(0) photoexcitation. Time-resolved emission was measured in the whole visible region, and the lifetimes, intrinsic emission spectra, and radiative lifetimes of the transients were obtained by quantitative analysis. It was concluded that the initially populated S(2) state is relaxed with a time constant of 45 fs to generate the S1 state retaining the perpendicular structure, and the D(2d) --> D(2) structural change (the change of the dihedral angle between the two ligand planes) occurs in the S(1) state with a time constant of 660 fs. The intersystem crossing from the S(1) state to the T(1) state takes place after this structural distortion with a time constant of 7.4 ps. Importantly, the temporal spectral evolution relevant to the structural change clearly exhibited an isoemissive point around 675 nm. This manifests that there exists a shallow potential minimum at the perpendicular geometry on the S1 surface, and the S1 state stays undistorted for a finite period as long as 660 fs before the structural distortion. This situation is not expected for the structural change induced by the ordinary (pseudo-)Jahn-Teller effect, because the distortion should be induced by the spontaneous structural instability at the perpendicular structure. This result sheds new light on the present understanding on the structural change occurring in the metal complexes.