NMR studies of chloroform@cryptophane-A and chloroform@bis-cryptophane inclusion complexes oriented in thermotropic liquid crystals

Oriented inclusion complexes of chloroform@cryptophane-A and chloroform@bis-cryptophane were prepared using a nematic thermotropic liquid crystal (ZLI 1132), and the alignment and magnetic resonance properties of these host-guest systems were studied via ¹³C NMR of the labeled guests. Large ¹H-¹³C dipolar splittings for ¹³CHCl₃ guests indicated significantly enhanced (∼2-fold) ordering for the trapped vs. free ligands under all conditions studied, with similar ordering observed for the two complexes - despite significant differences in size and motional freedom between the hosts. For each environment, variable-temperature studies permitted the sign and magnitude of the order parameter for chloroform's C-H bond to be independently determined from the ¹³C chemical shift anisotropy (CSA) shifts (via the gradient method) and the restored ¹H-¹³C dipolar couplings. In both systems, the results are consistent with overall alignment of the complexes such that the cage principal axis lies roughly perpendicular to the LC director.