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Two, acyclic (1) and cyclic (2), steroidal
molecular rotors containing 1,4-diethynyl-2,3-difluoro-phenylene units
as rotators were investigated by means of single crystal X-ray diffraction,
high resolution solid state NMR spectroscopy, and computer methods.
The aim of this study was to understand and search for a correlation
between the size of difluoro-phenylene units and free space in the
crystal lattice required for molecular reorientation as well as the
topology and time scale of dynamic processes. As a primary tool for
analysis of molecular motions in the solid state, 1H–13C PISEMA, a technique which allows following the dynamics
in the range of 10–3–10–6 s, was employed. The PISEMA data defining the 1H–13C dipolar couplings, whose values are sensitive to local
motion, were confronted with 13C CSA parameters. Our studies
revealed that replacing hydrogen by fluorine in acyclic rotors has
significant consequences for dynamic processes. In the case of hydrogen-substituted
species, free rotation around the 1–4 axis of the benzene ring
was proven. For fluorine derivatives 1, only small amplitude
wobbling of aromatic residues was observed. The only large amplitude
reorientation, a so-called π-jump around the 1–4 axis,
was observed during the phase transition related with solvent migration
from the crystal lattice. For cyclic rotors (2) two crystallographic
forms 2A (triclinic, P1 space group)
and 2B (monoclinic, P21 space
group) are established. The form 2B containing a heptane
molecule in the crystal lattice undergoes a thermal transition with
large amplitude motion of building units of the steroidal frame. The
high dynamics of the fluorinated rotator for 2A is proven.
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