Azatriangulene-Based Conductive C═C Linked Covalent Organic Frameworks with Near-Infrared Emission.

Hamzehpoor, Ehsan; Ghamari, Pegah; Tao, Yuze; Rafique, Muhammad Ghufran; Zhang, Zhenzhe; Salehi, Mahdi; Stein, Robin S; Ramos-Sanchez, Jorge et al. · Adv Mater · 2024

basic_science · Level V

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Abstract

Two near-infrared (NIR) emissive π-conjugated covalent organic frameworks (COFs) pTANG1 and pTANG2 are synthesized using Knoevenagel condensation of trioxaazatriangulenetricarbaldehyde (TATANG) with benzene- and biphenyldiacetonitriles, respectively. The morphology of the COFs is affected by the size of TATANG precursor crystals. Donor-acceptor interactions in these COFs result in small bandgaps (≈1.6 eV) and NIR emission (λ<sub>max</sub> = 789 nm for pTANG1). pTANG1 can absorb up to 9 molecules of water per unit cell, which is accompanied by a marked quenching of the NIR emission, suggesting applications as humidity sensors. p-Doping with magic blue significantly increases the electrical conductivities of the COFs by up to 8 orders of magnitude, with the room temperature conductivity of pTANG1 reaching 0.65 S cm<sup>-1</sup>, the highest among reported C═C linked COFs. <sup>1</sup>H NMR relaxometry, temperature-dependent fluorescence spectroscopy, and DFT calculations reveal that the higher rigidity of the shorter phenylene linker is responsible for the more extended conjugation (red-shifted emission, higher electrical conductivity) of pTANG1 compared to pTANG2.