Spin alignment of pseudo two-dimensional poly(aminiumtriphenylene)

A room temperature high-spin arylaminium radical polymer satisfying a non-Kekulé and non-disjoint structure was designed and synthesized. A tris(dianisylaminium)triphenylene 3 was synthesized through the oxidative trimerization, the palladium catalyzed amination, and chemical oxidation. The SQUID and NMR shift measurement indicated a quartet state (S = 3/2) for 3 from 2 to 330 K. A model compound 3 was extended to a pseudo two-dimensional poly[anisylaminotris(hexyloxy)triphenylene] 1. Copolycondensation of 2,6,10-tribromo-3,7,11-tris(hexyloxy)triphenylene 4 and 2,6,10-tris(p-anisyl- amino)-3,7,11-tris(hexyloxy)triphenylene 5 using the palladium catalyst gave the polymer 6 with M_n = 5400. This precursor 6 was oxidized to the corresponding polyradical 1. In Χ^T values plots, the maximum Χ^T value at 3.5 K was 1.38, theoretical value of S = 9/2 is 1.375. These results indicated spin-alignment of the polyradical 1 through the pseudo two-dimensional structure.