RESUMEN
Intersystem crossing (ISC) rates of transition-metal complexes are determined by the complex interplay of a molecule's electronic and structural dynamics. To broaden our understanding of these key factors, we investigate the case of the prototypical d8-d8 dimetal complex [Pt(ppy)(µ-tBu2pz)]2 using broad-band transient absorption anisotropy in combination with ultrafast fluorescence up-conversion and ab initio calculations. We find that, upon excitation of the molecule's metal-metal-to-ligand charge-transfer transition, ISC occurs in hundreds of femtoseconds from the lowest excited singlet state S1 to the triplet state T2, from where the energy relaxes to the lowest energy triplet state T1. ISC to the T2 state, rather than T1, is further rationalized through supporting arguments. Observed vibrational coherences along the Pt-Pt mode are attributed to the formation of nuclear wavepackets on the ground and excited electronic states that dephase prior to ISC because of the structural flexibility of the complex. Beyond demonstrating the relationship between the energy relaxation and structural dynamics of [Pt(ppy)(µ-tBu2pz)]2, our results provide new insights into the photoinduced dynamics of d8-d8 dimetal complexes more generally.
RESUMEN
The excited-state dynamics of a donor-acceptor dyad composed of 1-propyl-2-pyridinyl-benzimidazole (PPBI) as donor and the photochromic molecular switch diphenylnaphthopyran (DPNP) as acceptor linked via an ester bridge has been investigated by a combination of static and time-resolved spectroscopies and quantum chemical calculations. The UV absorption spectrum of the dyad is virtually identical to the sum of the spectra of its individual constituents, indicating only weak electronic coupling between the donor and acceptor in the electronic ground state. After selective photoexcitation of the PPBI chromophore in the dyad at λpump = 310 nm, however, a fast electronic energy transfer (EET) from the donor to the acceptor is observed, by which the lifetime of the normally long-lived excited state of PPBI is reduced to a few ps. Enabled by the EET, the acceptor switches from its ring-closed naphtopyran form to its ring-opened merocyanine form. The singular value decomposition-based global analyses of the measured femtosecond time-resolved transient absorption spectra of the dyad and its two building blocks as reference compounds allowed us to determine a value for the EET time constant in the dyad of τ = 2.90 ± 0.60 ps. For comparison, Förster theory predicts characteristic FRET times between 1.2 ps ≤ τ ≤ 4.2 ps, in good agreement with the experimental result.
RESUMEN
We report on the ultrafast photodynamics of an iron(II) complex with a photoisomerizable pentadentate azo-tetrapyridylamino ligand after irradiation with ultraviolet light. The results of femtosecond transient electronic absorption spectroscopy performed on the low-spin (LS) form of the title complex show that initial excitation of the ππ* state of the azopyridine unit in the ligand at λpump = 312 nm is followed by an ultrafast intersystem crossing (ISC) that leads to the formation of a metal-centered (MC) 5T state, in competition with the intended photoswitching of the azopyridine unit. Additional measurements carried out upon excitation of the singlet metal-to-ligand charge-transfer (1MLCT) transition at λpump = 455 nm suggest that this energy transfer occurs via an MLCT state. The resulting high-spin (HS) 5T state of the complex is metastable and recovers to the LS ground state with a time constant of â¼3 ns. The implications of these observations on the ligand-driven light-induced spin change concept are discussed.