Synthesis, Structures, and Electronic Properties of 2,7-Anthrylene-Based Azacyclophanes Bearing -, -, and -Phenylenediamine Linkers.

A series of novel azacyclophanes consisting of 2,7-anthrylene and phenylene units were designed and synthesized by the Buchwald-Hartwig coupling reaction to investigate their unique electronic properties in multiple oxidized states. Cyclic voltammetry showed that the -phenylene derivative exhibited three reversible oxidation waves, whereas the - and -phenylene derivatives showed two quasi-reversible oxidation waves due to the complicated intramolecular interaction between the oxidized units and neutral units. Moreover, the absorption spectra of the -phenylene derivative in different oxidation states showed absorption bands at 865 and 1025 nm, which were attributed to intramolecular charge-transfer interactions. The photophysical and electrochemical properties of the -phenylene analog were also compared with those of the - and -phenylene derivatives based on theoretical calculations for further evaluation of the intramolecular electronic interactions.