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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 (E g ≈ 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).

N,N′-Bicarbazole with almost spatially vertical structure was synthesized by a facile method and was demonstrated as a versatile building block for conjugated microporous polymers (CMPs) through transition metal catalyzed coupling polymerizations including Yamamoto, Suzuki, and Sonogashira polymerizations. The porosities and morphologies of four N,N′-bicarbazole-based CMPs were systematically studied and compared. With high surface area, good thermal stability and microporous structure, the CMP synthesized by Yamamoto polymerization exhibited excellent adsorption capacities of CO 2 and organic dyes, and the maximum adsorption capacity of methylene blue (MB) in water reached up to 1016 mg g −1 . The good adsorption properties of N,N′-bicarbazole CMPs could be a good candidate for potential applications in water purification and treatment.