Calix[4]arene-Based Bis(Nitric Oxide) Complexes: Synthesis, Physical Properties, and Structural Characterization.

Calix[4]arene-based molecules hold great promise as candidate sensors and storage materials for nitric oxide (NO), owing to their unprecedented binding affinity for NO. However, the structure of calix[4]arene is complicated by the availability of four possible conformers: 1,3-alternate, 1,2-alternate, cone, and partial cone (paco). Whilst complexes of NO with several of these conformers have previously been established, the 1,2-alternate conformer complex, that is, [1,2-alter⋅NO]+ , has not been previously reported. Herein, we determine the crystal structure of the NO complex with the 1,2-alternate conformer for the first time. In addition, we have also found that the 1,2-alternate and 1,3-alternate conformers can combine with two NO molecules to form stable bis(nitric oxide) complexes. These new complexes, which exhibit remarkable binding capacity for the construction of NO-storage molecules, were characterized by using X-ray crystallography and NMR, IR, and UV/Vis spectroscopy. These findings will extend our understanding of the interactions between nitric oxide and cofacially and non-cofacially arrayed aromatic rings, and we expect them to aid in the design and development of new supramolecular sensors and storage materials for NO with high capacity and efficacy.