Integrating Tetrathiafulvalene and Nickel‐Bis(dithiolene) Units into Donor‐Acceptor Covalent Organic Frameworks for Stable and Efficient Photothermal Conversion

Abstract

Tetrathiafulvalene (TTF) and Ni‐bis(dithiolene) are typical conductive units widely studied in electronics, optics, and photochemistry. However, their applications in near‐infrared (NIR) photothermal conversion are often limited by insufficient NIR absorption and low chemical/thermal stability. Herein, we integrate TTF and Ni‐bis(dithiolene) into a covalent organic framework (COF) with stable and efficient NIR and solar photothermal conversion performance. Two isostructural COFs, namely Ni‐TTF and TTF‐TTF, are successfully isolated which are composed of TTF and Ni‐bis(dithiolene) units as donor‐acceptor (D−A) pairs or TTF units only. Both COFs show high BET surface areas and good chemical/thermal stability. Notably, compared with TTF‐TTF, the periodic D−A arrangement in Ni‐TTF significantly lowers the bandgap, leading to unprecedented NIR and solar photothermal conversion performance.

A robust conductive covalent organic framework for ultra-stable potassium storage

“…1a). 29 The powder X-ray diffraction (PXRD) pattern of Ni-TTF exhibited a prominent peak at 5.3°, accompanied by minor peaks at 7.5°, 10.6°, 11.9°, 16.9°, and 26.0°. These peaks correspond to the crystallographic facets [110], [200], [220], [310], [240], and [001], respectively.…”

Tailoring Dynamic Chiral Supramolecular Assembly with Phototriggered Radical Anions of C3-Symmetric Triphenylene Triimides

“…In the chiral system, the diffraction peaks corresponded to crystalline phases with a rectangular geometry and a P222 space group (Figure S28b and Table S3). 62,63 The size of the unit cell was determined based on the values obtained from the diffraction pattern (Figure S28d). Interestingly, the arrangement of N-TTI and R-TTI with imide bonds contrasts with that of triphenylenebased mesogens, which self-assemble into a hexagonal columnar geometry.…”

“…In the chiral system, the diffraction peaks corresponded to crystalline phases with a rectangular geometry and a P 222 space group (Figure S28b and Table S3). , The size of the unit cell was determined based on the values obtained from the diffraction pattern (Figure S28d). Interestingly, the arrangement of N -TTI and R -TTI with imide bonds contrasts with that of triphenylene-based mesogens, which self-assemble into a hexagonal columnar geometry. , Because no diffraction peaks appeared in the low- q region of the SAXS pattern (Figure S29), it is estimated that N -TTI and R -TTI are cubic and complicated crystalline phases, respectively, based on the results obtained from the WAXS pattern.…”

Porous Crystalline Materials Based on Tetrathiafulvalene and Its Analogues: Assembly, Charge Transfer, and Applications

“…30 The CT between the donor (D) and acceptor (A) can enhance UV−vis-NIR absorption, thereby offering the potential for photothermal conversion. On the basis of this principle, CT Co-MOF (4) 31 and Zn-MOF (5) 32 and CT COF systems (TTF-TTF and NiS 4 -TTF) 33…”