High-Spin Polycations of a Trlaminobenzene

Abstract

Abstract Organic poly radical ions are molecular spin units which could be used in the construction of magnetic materials. They possess the feature of redox activation / deactivation, a potential means of reversibly controlling the molecular spin state of the unit, thus imparting a magnetic switch function. Here, we describe the prospect of preparing tris arylamines suitably structured to yield long-lived cation, dication, and trication states of successively higher spin mutiplicity. The preparation and oxidation of N,N,N′,N′,N″,N″-hexa-p-anisyl-1,3,5-triaminobenzene (HATAB) are discussed, along with the ESR spectra of the HATAB higher oxidation states. The HATAB2+ and HATAB3+ ESR signals are assigned to triplet and quartet states respectively which, on the basis of cursory Curie-Weiss data, are tentatively assigned as the ground states of these poly cations, consistent with calculational results (AMI/UHF)on the unsubstituted system, 1,3,5-triaminobenzene dication and trication.