A Corrole‐Based Covalent Organic Framework Featuring Desymmetrized Topology

Abstract

Herein, for the first time, we present the successful synthesis of a novel two‐dimensional corrole‐based covalent organic framework (COF) by reacting the unusual approximately T‐shaped 5,10,15‐tris(p‐aminophenyl)corrole H3TPAPC with terephthalaldehyde, which adopts desymmetrized hcb topology and consists of a staggered AB stacking structure with elliptical pores. The resultant corrole‐based COF, TPAPC‐COF, exhibits high crystallinity and excellent chemical stability. The combination of extended π‐conjugated backbone and interlayer noncovalent π–π interactions endows TPAPC‐COF with excellent absorption capability in the entire visible‐light and even near‐infrared regions. Moreover, this work suggests the promise of TPAPC‐COF as a new class of photoactive material for efficient singlet‐oxygen generation with potential photodynamic therapy application as demonstrated by in vitro anticancer studies.

Solving the COF trilemma: towards crystalline, stable and functional covalent organic frameworks

“…129 Nevertheless, there is a rich literature in asymmetric building blocks that have been used for COF design as well. 129,[137][138][139] Linkers with sp 3 -carbons are known as well and are especially prominent for tetrahedral building blocks based on tetraphenylmethane or adamantane. 4,9,65,[140][141][142][143][144][145] These building blocks are especially important for the construction of three-dimensional COFs, as the number of rigid three-dimensional nodes other than those mentioned above are generally limited.…”

Corroles and Hexaphyrins: Synthesis and Application in Cancer Photodynamic Therapy

“…Recently, the synthesis of a two-dimensional corrole-based covalent organic framework (COF) was developed. The corrole-based COF - 100 with desymmetrized structure was isolated in 86% yield from the [3 + 2] imine condensation reaction of the approximately T-shaped tris( p -aminophenyl)corrole ( 78 ) with the linear terephthaldehyde ( Scheme 36 ) [ 82 ]. COF - 100 demonstrated high chemical stability and permanent porosity, with a sphere-like morphology and a Brunauer–Emmett–Teller (BET) surface area of 745 m 2 /g.…”

Metal nanoparticles/carbon nanosheets-derived from covalent organic frameworks for electrochemical sensing furazolidone, dopamine and uric acid

“…XRD pattern of COF TD showed the characteristic peaks of (100), ( 200), ( 210) and (001) crystal planes at 3.29°, 5.3°, 7.21° and 25.1° (Fig. 1C), proving that the crystallinity of COF TD was good [29][30][31]. Next, the formation of COF TD was con rmed by Fourier transform infrared spectroscopy (FTIR) (Fig.…”