A Two-Dimensional Poly(azatriangulene) Covalent Organic Framework with Semiconducting and Paramagnetic States.

The black crystalline (aza)triangulene-based covalent organic framework TANG-COF was synthesized from its trinitro-TANG precursor via a one-pot, two-step reaction involving Pd-catalyzed hydrogenation and polycondensation with an aromatic dialdehyde. High crystallinity and permanent porosity of the layered two-dimensional (2D) structure were established. The rigid, electron-rich trioxaazatriangulene (TANG) building block enables strong π-electron interactions manifested in broad absorptions across the visible and NIR regions (Eg ≈ 1.2 eV). The high HOMO energy of TANG-COF (-4.8 eV) enables facile p doping, resulting in electrical conductivity of up to 10-2 S/cm and room-temperature paramagnetic behavior with a spin concentration of ∼10%. DFT calculations reveal dispersion of the highest occupied band both within the 2D polymer layers (0.28 eV) and along their π-stacked direction (0.95 eV).