A Triply Negatively Charged Nanographene Bilayer with Spin Frustration.

We report on the largest open-shell graphenic bilayer and also the first example of triply negatively charged radical π-dimer. Upon three-electron reduction, bilayer nanographene fragment molecule (C 96 H 24 Ar 6 ) 2 (Ar=2,6-dimethylphenyl) (1 2 ) was transformed to a triply negatively charged species 1 2 3 ⋅ - , which has been characterized by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy and magnetic properties on a superconducting quantum interference device (SQUID). 1 2 3 ⋅ - features a 96-center-3-electron (96c/3e) pancake bond with a doublet ground state, which can be thermally excited to a quartet state. It consists of 34 π-fused rings with 96 conjugated sp 2 carbon atoms. Spin frustration is observed with the frustration parameter f>31.8 at low temperatures in 1 2 3 ⋅ - , which indicates graphene upon reduction doping may behave as a quantum spin liquid.