Solid-State NMR and Diffraction Studies of a Tunable p-tert-Butylcalix[4]arene·Guest Structure

The majority of p - tert -butylcalix[4]arene inclusion compounds are 4-fold symmetric in the solid state, with the guest molecular and the host symmetry axes approximately aligned. In contrast, nitrobenzene (and related guests) induces a permanent symmetry-reducing distortion of the p - tert -butylcalix[4]arene compound and occupies a position in which the guest molecular axis is no longer aligned with that of the host. These compounds have been characterized by single-crystal X-ray diffraction as well as 13 C CP-MAS and 2 H NMR in the solid state. Introduction of propane as a second, minority guest in sufficient quantities induces the alignment of the nitrobenzene molecular axis with the host C 4 symmetry axis. Nitrobenzene- d 5 guest dynamics in the symmetric and asymmetric structures reveal a much stronger host·guest interaction in the latter. The nature of the asymmetry is due to a cooperative effect rather than any intrinsic property of the individual p - tert -butylcalix[4]arene·guest units. In general, this work give initial insight into the suitability of the p - tert -butylcalixarene[4]arene framework for crystal engineering and illustrates the close connection between dynamics and lattice symmetry and structure.