Rational Design of an Air-Stable, High-Spin Diradical with Diazapyrene

Stable carbon-based polyradicals exhibiting strong spin-spin coupling and slow depolarization processes are particularly attractive functional materials. A new molecular motif synthesized by a convenient method that allows the integration of stable, high-spin radicals to (hetero)aromatic polycycles has been developed, as illustrated by a non-Kekule diradical showing a triplet ground state with long persistency (tau 1/2 approximate to 31 h) in air. Compared to the widely used 1,3-phenylene, the newly designed (diaza)pyrene-4,10-diyl moiety is for the first time demonstrated to confer ferromagnetic (FM) spin coupling, allowing delocalized non-disjoint SOMOs. With the X-ray crystallography unambiguously proving the diradical structure, the triplet ground state was thoroughly characterized. A large Delta ES-T of 1.1 kcal/mol, proving the strong FM coupling effect, was revealed consistently by superconducting quantum interference device (SQUID) measurements and variable-temperature electron paramagnetic resonance (EPR) spectroscopy, while the zero-field splitting and triplet nutation characters were examined by continuous-wave and pulsed EPR spectroscopy. A millisecond spin-lattice relaxation time was also detected. The current study not only offers a new molecular motif enabling FM coupling between carbon-based spins, but more importantly presents a general method for installing stable polyradicals into functional pi-systems. A general method has been developed for installing stable polyradicals into polycyclic pi-systems, as illustrated by the formation of an air-stable, high-spin carbon-based diradical with a new ferromagnetic coupling motif of diazapyrene. The structure of the diradical was confirmed by X-ray diffraction, while the magnetic measurements provided unambiguous evidence for the high-spin ground state and a long spin relaxation process.+image