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- ItemMetallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer(Cambridge : RSC, 2021) Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H.M.; Wang, Xue-Bin; Advoshenko, Stanislav M.; Popov, Alexey A.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 YxSc3−xN@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.
- ItemUltrafast nonlocal collective dynamics of Kane plasmon-polaritons in a narrow-gap semiconductor(Washington : American Association for the Advancement of Science (A A A S), 2019) Charnukha, A.; Sternbach, A.; Stinson, H.T.; Schlereth, R.; Brüne, C.; Molenkamp, L.W.; Basov, D.N.The observation of ultrarelativistic fermions in condensed-matter systems has uncovered a cornucopia of novel phenomenology as well as a potential for effective ultrafast light engineering of new states of matter. While the nonequilibrium properties of two- and three-dimensional (2D and 3D) hexagonal crystals have been studied extensively, our understanding of the photoinduced dynamics in 3D single-valley ultrarelativistic materials is, unexpectedly, lacking. Here, we use ultrafast scanning near-field optical spectroscopy to access and control nonequilibrium large-momentum plasmon-polaritons in thin films of a prototypical narrow-bandgap semiconductor Hg0.81Cd0.19Te. We demonstrate that these collective excitations exhibit distinctly nonclassical scaling with electron density characteristic of the ultrarelativistic Kane regime and experience ultrafast initial relaxation followed by a long-lived highly coherent state. Our observation and ultrafast control of Kane plasmon-polaritons in a semiconducting material using light sources in the standard telecommunications fiber-optics window open a new avenue toward high-bandwidth coherent information processing in next-generation plasmonic circuits.