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Real-time capture of nuclear motions influencing photoinduced electron transfer.

ABSTRACT: Although vibronic coupling phenomena have been recognized in the excite state dynamics of transition metal complexes, its impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor-acceptor complex featuring a cyclometalated Pt(ii) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(ii) dimer electron donor, ultrafast broadband transient absorption spectroscopy revealed direct modulation of NDI radical anion formation through certain CWP motions and correlated temporal evolutions of the amplitudes for these CWPs with the NDI radical anion formation. These results provide clear evidence that the CWP motions are the vibronic coherences coupled to the PET reaction coordinates. Normal mode analysis identified that the CWP motions originate from vibrational modes associated with the dihedral angles and bond lengths between the planes of the cyclometalating ligand and the NDI, the key modes altering their π-interaction, consequently influencing PET dynamics. The findings highlight the pivotal role of vibrations in shaping the favorable trajectories for the efficient PET processes.

SUBMITTER: Kim P

PROVIDER: S-EPMC11339639 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Real-time capture of nuclear motions influencing photoinduced electron transfer.

Kim Pyosang P Roy Subhangi S Valentine Andrew J S AJS Liu Xiaolin X Kromer Sarah S Kim Tae Wu TW Li Xiaosong X Castellano Felix N FN Chen Lin X LX

Chemical science 20240822

Although vibronic coupling phenomena have been recognized in the excite state dynamics of transition metal complexes, its impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor-acceptor complex featuring a cyclometalated Pt(ii) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(ii) dimer electron donor, ultrafast broad ...[more]

PMID: 39184296

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Project description:We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc3-x N@C80 (x = 0-3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1-T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin-lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

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Real-time capture of nuclear motions influencing photoinduced electron transfer.

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Real-time capture of nuclear motions influencing photoinduced electron transfer.

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