Chiral π-Conjugated Double Helical Aminyl Diradical with the Triplet Ground State

We describe effective development of the highly diastereo-selective synthesis of double helical tetraamine 2-H-2-C-2 and propose a mechanism for its formation. The resolution of 2-H-2-C-2 is facilitated by a high racemization barrier of 43 kcal mol(-1) and it is implemented via either a chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation of the first high-spin neutral diradical, with spin density delocalized within an enantiomeric double helical pi-system. The presence of two effective 3-electron C-N bonds in the diradical leads to: (1) the triplet (S = 1) high-spin ground state with a singlet-triplet energy gap of 0.4 kcal mol(-1) and (2) the long half-life of up to 6 days in 2-MeTHF at room temperature. The diradical possesses a racemization barrier of at least 26 kcal mol(-1) in 2-MeTHF at 293 K and chiroptical properties, with an absorption anisotropy factor |g| approximate to 0.005 at 548 nm. These unique magnetic and optical properties of our diradical form the basis for the development of next-generation spintronic devices.