Isolable Triradical Trication of Hexaaza[16]paracyclophane with Embedded 9,10-Anthrylenes: A Frustrated Three-Spin System.
Ryohei KurataDaisuke SakamakiMasashi UebeMariko KinoshitaTetsuo IwanagaTakashi MatsumotoAkihiro ItoPublished in: Organic letters (2017)
A new derivative of hexaaza[16]paracyclophane in which p-phenylenes are alternately replaced by 9,10-anthrylenes was prepared to investigate the impact on overall π-conjugation as well as conformational change of the macrocycle. The charge and spin distribution for one-electron and three-electron oxidation of the macrocycle was elucidated by means of electrochemical, spectroelectrochemical, EPR spectroscopic, and SQUID magnetometric methods. In particular, the triradical trication was successfully isolated as an air-stable salt, and moreover, its structure was disclosed by X-ray analysis. The triradical trication was characterized as a spin-frustrated three-spin system with the antiferromagnetic exchange interaction (J/kB ≃ - 74 K).