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- ItemQuinoidal Azaacenes: 99 % Diradical Character(Weinheim : Wiley-VCH Verlag, 2020) Intorp, S.N.; Hodecker, M.; Müller, M.; Tverskoy, O.; Rosenkranz, M.; Dmitrieva, E.; Popov, A.A.; Rominger, F.; Freudenberg, J.; Dreuw, A.; Bunz, U.H.F.Quinoidal azaacenes with almost pure diradical character (y=0.95 to y=0.99) were synthesized. All compounds exhibit paramagnetic behavior investigated by EPR and NMR spectroscopy, and SQUID measurements, revealing thermally populated triplet states with an extremely low-energy gap ΔEST′ of 0.58 to 1.0 kcal mol−1. The species are persistent in solution (half-life≈14–21 h) and in the solid state they are stable for weeks.
- ItemMagnetic anisotropy of endohedral lanthanide ions: paramagnetic NMR study of MSc2N@C80-Ih with M running through the whole 4f row(Cambridge : RSC, 2015) Zhang, Y.; Krylov, D.; Rosenkranz, M.; Schiemenz, S.; Popov, A. A.Paramagnetic and variable temperature 13C and 45Sc nuclear magnetic resonance studies are performed for nitride clusterfullerenes MSc2N@C80 with icosahedral Ih(7) carbon cage, where M runs through all lanthanides forming nitride clusters. The influence of the endohedral lanthanide ions on the NMR spectral pattern is carefully followed, and dramatic differences are found in peak positions and line widths. Thus, 13C lines broaden from 0.01–0.02 ppm in diamagnetic MSc2N@C80 molecules (M = La, Y, Lu) to several ppm in TbSc2N@C80 and DySc2N@C80. Direction of the paramagnetic shift depends on the shape of the 4f electron density in corresponding lanthanide ions. In TmSc2N@C80 and ErSc2N@C80 with prolate 4f-density of lanthanide ions, 13C signals are shifted down-field, whereas 45Sc peaks are shifted up-field versus diamagnetic values. In all other MSc2N@C80 molecules lanthanide ions have oblate-shaped 4f electron density, and the lanthanide-induced shift is negative for 13C and positive for 45Sc peaks. Analysis of the pseudocontact and contact contributions to chemical shifts revealed that the pseudocontact term dominates both in 13C and 45Sc NMR spectra, although contact shifts for 13C signals are also considerable. Point charge computations of the ligand field splitting are performed to explain experimental results, and showed reasonable agreement with experimental pseudocontact shifts. Nitrogen atom bearing large negative charge and located close to the lanthanide ion results in large magnetic anisotropy of lanthanide ions in nitride clusterfullerenes with quasi-uniaxial ligand field.
- ItemSuppression of nematicity by tensile strain in multilayer FeSe/SrTiO3 films(College Park, MD : APS, 2023) Lou, Rui; Suvorov, Oleksandr; Grafe, Hans-Joachim; Kuibarov, Andrii; Krivenkov, Maxim; Rader, Oliver; Büchner, Bernd; Borisenko, Sergey; Fedorov, AlexanderThe nematicity in multilayer FeSe/SrTiO3 films has been previously suggested to be enhanced with decreasing film thickness. Motivated by this, there have been many discussions about the competing relation between nematicity and superconductivity. However, the criterion for determining the nematicity strength in FeSe remains highly debated. The understanding of nematicity as well as its relation to superconductivity in FeSe films is therefore still controversial. Here, we fabricate multilayer FeSe/SrTiO3 films using molecular beam epitaxy and study the nematic properties by combining angle-resolved photoemission spectroscopy, Se77 nuclear magnetic resonance, and scanning tunneling microscopy experiments. We unambiguously demonstrate that, near the interface, the nematic order is suppressed by the SrTiO3-induced tensile strain; in the bulk region further away from the interface, the strength of nematicity recovers to the bulk value. Our results not only solve the recent controversy about the nematicity in multilayer FeSe films, but also offer valuable insights into the relationship between nematicity and superconductivity.