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  1. ChemPhysChem (Ed.)
    Abstract

    Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6Se8(PEt3)6. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6Se8] core while ligands function as an insulated shell.59Co SSNMR measurements on the core and31P,13C on the ligands show that the neutral Co6Se8(PEt3)6is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6Se8(PEt3)6]+1is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.

     
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    Free, publicly-accessible full text available January 15, 2025
  2. Free, publicly-accessible full text available January 18, 2025
  3. Abstract

    Exciton polaritons are quasiparticles of photons coupled strongly to bound electron-hole pairs, manifesting as an anti-crossing light dispersion near an exciton resonance. Highly anisotropic semiconductors with opposite-signed permittivities along different crystal axes are predicted to host exotic modes inside the anti-crossing called hyperbolic exciton polaritons (HEPs), which confine light subdiffractionally with enhanced density of states. Here, we show observational evidence of steady-state HEPs in the van der Waals magnet chromium sulfide bromide (CrSBr) using a cryogenic near-infrared near-field microscope. At low temperatures, in the magnetically-ordered state, anisotropic exciton resonances sharpen, driving the permittivity negative along one crystal axis and enabling HEP propagation. We characterize HEP momentum and losses in CrSBr, also demonstrating coupling to excitonic sidebands and enhancement by magnetic order: which boosts exciton spectral weight via wavefunction delocalization. Our findings open new pathways to nanoscale manipulation of excitons and light, including routes to magnetic, nonlocal, and quantum polaritonics.

     
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  4. Abstract

    Magnetic van der Waals heterostructures provide a unique platform to study magnetism and spintronics device concepts in the 2D limit. Here, studies of exchange bias from the van der Waals antiferromagnet CrSBr acting on the van der Waals ferromagnet Fe3GeTe2(FGT) are reported. The orientation of the exchange bias is along the in‐plane easy axis of CrSBr, perpendicular to the out‐of‐plane anisotropy of the FGT, inducing a strongly tilted magnetic configuration in the FGT. Furthermore, the in‐plane exchange bias provides sufficient symmetry breaking to allow deterministic spin–orbit torque switching of the FGT in CrSBr/FGT/Pt samples at zero applied magnetic field. A minimum thickness of the CrSBr of >10 nm is needed to provide a non‐zero exchange bias at 30 K.

     
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