LAUSR

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