Acetonitrile inclusion complexes of piperazine‐based macrocycles

New piperazine‐based macrocycles with single small cavities were prepared by using high dilution technique. The inclusion of acetonitrile into the cavity (7, 8) or clathrate formation (3) was studied by 1H‐NMR spectroscopy in solution and by X‐ray diffraction in the crystalline state. The cycle 3 forms a molecular cleft, a molecular pocket, where the acetonitrile molecule is held by four weak N…︁H interactions reinforcing the clathrate formation. The cycles 7 and 8 contain a rigid cavity for an exact sterical fit with the methyl group of a linear compound like acetonitrile. The acetonitrile inclusion complex with 7 proved to be stable under normal conditions and was studied by means of thermogravimetry. It is stable up to 80°C and the breakdown is complete when the temperature is raised over 120°C. Solid‐state IR studies show a shift of the cyano band of 5 cm−1 to smaller wave numbers when compared with free acetonitrile. The acetonitrile methyl group is shielded and in the 1H‐NMR spectrum its signal is shifted to δ = 1.85.