| Abstract: | Reported here are the syntheses, conformational structures, electrochemical properties, and noncovalent anion binding of corona5]arenes. A (3+2) fragment coupling reaction proceeded efficiently under mild reaction conditions to produce a number of novel heteroatom‐ and methylene‐bridged corona3]arene2]tetrazine macrocycles. Selective oxidation of the sulfur atom between two phenylene rings afforded sulfoxide‐ and sulfone‐linked corona5]arenes in good yields. All corona5]arenes synthesized adopted similar 1,2,4‐alternate conformational structures, forming pentagonal cavities. The cavity sizes and the electronic properties such as redox potentials, were measured with CV and DPV, and were influenced by the different bridging units. As electron‐deficient macrocycles, the acquired corona3]arene2]tetrazines served as highly selective hosts, forming complexes with the hydrogen‐bonded dimer of dihydrogen phosphate through cooperative anion–π interactions. |
