Effiziente thermisch aktivierte verzögerte Fluoreszenz in endohedralen Metallofullerenen
Zusammenfassung der Projektergebnisse
The project was aimed at the advanced understanding of photoluminescent properties of metallofullerenes, including the influence of the composition of endohedral species on the photophysical properties. Particular focus was the phenomenon of thermally-activated delayed fluorescence discovered in fullerene Y3N@C80. We performed comprehensive variable-temperature, steady-state and timeresolved studies of luminescence in a series of metallofullerenes, such as YxSc3–xN@C80, chemical derivatives of Y3N@C80 with different addition motifs, and Nd-based metallofullerenes. In the series of YxSc3–xN@C80 compounds, we found a strong variation of the emission energy depending on the cluster composition. The more Sc atoms are present in the cluster, the further into near-infrared range its emission is shifted. Likewise, the energy difference between singlet and triplet excited state, and luminescence lifetimes decreased when ore Sc atoms were present. These changes were interpreted by the phenomenon of the photo-switching, in which position of the cluster inside the fullerene changed after photon absorption. The studies of the triplet state by light-induced electron paramagnetic resonance spectroscopy allowed to understand how spin density is distributed between the fullerene and metal atoms. Another important finding of the project was the first observation of Nd-based luminescence in Nd metallofullerenes, NdSc2N@C80, NdLu2N@C80, and NdY2N@C80. We found that the internal strain experienced by the NdM2N cluster inside the fullerene caused a strong nephelauxetic effect, indicating that degree of covalency in Nd bonding is unusually high. At the same time, the spectra exhibited fine structure of the emission bands, evidencing the unprecedentedly strong ligand-field splitting.
Projektbezogene Publikationen (Auswahl)
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Addition of CF2 group to endohedral fullerene Sc3N@Ih-C80. Dalton Transactions, 49(26), 9137-9147.
Pykhova, Anastasia D.; Semivrazhskaya, Olesya O.; Samoylova, Nataliya A.; Rybalchenko, Alexey V.; Rosenkranz, Marco; Ioffe, Ilya N.; Popov, Alexey A. & Goryunkov, Alexey A.
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Tunable Fulleretic Sodalite MOFs: Highly Efficient and Controllable Entrapment of C60 Fullerene via Mechanochemistry. Chemistry of Materials, 32(24), 10628-10640.
Martinez, Valentina; Karadeniz, Bahar; Biliškov, Nikola; Lončarić, Ivor; Muratović, Senada; Žilić, Dijana; Avdoshenko, Stanislav M.; Roslova, Maria; Popov, Alexey A. & Užarević, Krunoslav
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Metallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer. Chemical Science, 12(22), 7818-7838.
Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H. M.; Wang, Xue-Bin; Avdoshenko, Stanislav M. & Popov, Alexey A.
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Temperature-dependent dynamics of endohedral fullerene Sc2@C80(CH2Ph) studied by EPR spectroscopy. Physical Chemistry Chemical Physics, 23(33), 18206-18220.
Kandrashkin, Yuri E.; Zaripov, Ruslan B.; Liu, Fupin; Büchner, Bernd; Kataev, Vladislav & Popov, Alexey A.
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Monometallic Endohedral Azafullerene. Journal of the American Chemical Society, 144(47), 21587-21595.
Xiang, Wenhao; Jiang, Xiaole; Yao, Yang-Rong; Xin, Jinpeng; Jin, Huaimin; Guan, Runnan; Zhang, Qianyan; Chen, Muqing; Xie, Su-Yuan; Popov, Alexey A. & Yang, Shangfeng
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Regioselective CF2 functionalization of Sc3N@D3h(5)-C78. Dalton Transactions, 51(3), 1182-1190.
Pykhova, Anastasia D.; Semivrazhskaya, Olesya O.; Samoylova, Nataliya A.; Popov, Alexey A.; Ioffe, Ilya N. & Goryunkov, Alexey A.
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Vibrational anatomy of C90, C96, and C100 fullertubes: probing Frankenstein's skeletal structures of fullerene head endcaps and nanotube belt midsection. Nanoscale, 14(30), 10823-10834.
Schiemenz, Sandra; Koenig, Ryan M.; Stevenson, Steven; Avdoshenko, Stanislav M. & Popov, Alexey A.
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Improving the molecular spin qubit performance in zirconium MOF composites by mechanochemical dilution and fullerene encapsulation. Chemical Science, 14(35), 9389-9399.
Vujević, Lucija; Karadeniz, Bahar; Cindro, Nikola; Krajnc, Andraž; Mali, Gregor; Mazaj, Matjaž; Avdoshenko, Stanislav M.; Popov, Alexey A.; Žilić, Dijana; Užarević, Krunoslav & Kveder, Marina
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Photoluminescence spectroscopy of dibenzopentacene single-crystals: multiple emissive states across temperature, time, and magnetic field in a pursuit of exothermic singlet fission. Journal of Materials Chemistry C, 11(37), 12714-12729.
Rosenkranz, Marco; Graf, Lukas; Büchner, Bernd; Knupfer, Martin & Popov, Alexey A.
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Using internal strain and mass to modulate Dy⋯Dy coupling and relaxation of magnetization in heterobimetallic metallofullerenes DyM2N@C80and Dy2MN@C80(M = Sc, Y, La, Lu). Inorganic Chemistry Frontiers, 10(2), 468-484.
Hao, Yajuan; Velkos, Georgios; Schiemenz, Sandra; Rosenkranz, Marco; Wang, Yaofeng; Büchner, Bernd; Avdoshenko, Stanislav M.; Popov, Alexey A. & Liu, Fupin
