A new tetragonal (P42(1)2) crystalline form of [Cr8F8Piv16] (HPiv = pivalic acid, trimethyl acetic acid) is reported. The ring-shaped molecules, which are aligned in a parallel fashion in the unit cell, form almost perfectly planar, regular octagons. The interaction between the CrIII ions is antiferromagnetic (J = 12 cm(-1)) which results in a S = 0 spin ground state. The low-lying spin excited states were investigated by cantilever torque magnetometry (CTM) and high-frequency EPR (HFEPR). The compound shows hard-axis anisotropy. The axial zero-field splitting (ZFS) parameters of the first two spin excited states (S = 1 and S = 2, respectively) are D1 = 1.59(3) cm(-1) or 1.63 cm(-1) (from CTM and HFEPR, respectively) and D2 = 0.37 cm(-1) (from HFEPR). The dipolar contributions to the ZFS of the S = 1 and S = 2 spin states were calculated with the point dipolar approximation. These contributions proved to be less than the combined single-ion contributions. Angular overlap model calculations that used parameters obtained from the electronic absorption spectrum, showed that the unique axis of the single-ion ZFS is at an angle of 19.3(1) degrees with respect to the ring axis. The excellent agreement between the experimental and the theoretical results show the validity of the used methods for the analysis of the magnetic anisotropy in antiferromagnetic CrIII rings.
We demonstrate that stacking layered materials allows a strain engineering where each layer is strained independently, which we call heterostrain. We combine detailed structural and spectroscopic measurements with tight-binding calculations to show that small uniaxial heterostrain suppresses Dirac cones and leads to the emergence of flat bands in twisted graphene layers (TGLs). Moreover, we demonstrate that heterostrain reconstructs, much more severely, the energy spectrum of TGLs than homostrain for which both layers are strained identically, a result which should apply to virtually all van der Waals structures opening exciting possibilities for straintronics with 2D materials.
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