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.

Single‐Pore versus Dual‐Pore Bipyridine‐Based Covalent–Organic Frameworks: An Insight into the Heterogeneous Catalytic Activity for Selective CH Functionalization

“…[35,[61][62][63] Ni-DBA-2D-COF and Ni-DBA-3D COF provide rare example of Ni(0) binding with π-electron conjugated dehydrobenzoannulene (DBA) motifs. [64,65] Mono and bimetallic postsynthetic modification of COFs increase catalyst life time and activity, for instance, Rh I /Pd II COF, corrole COF, and M/Salen-COF serve as reusable catalyst for cascade reactions, [66] photodynamic therapy, [67] and Henry reaction, [68] respectively. In addition, molybdenum-doped COF (Mo-COF) serve as a nanochannel-reactor for cyclohexene epoxidation with 99% conversion and over 70% selectivity.…”

Nanoscale covalent organic frameworks as theranostic platforms for oncotherapy: synthesis, functionalization, and applications

“…By loading 1 O 2 -unstable indocyanine green (ICG) uorescent dye into the pore of the TphDha COF shell, the in situ monitoring of1 O 2 location and therapeutic response could be achieved in vivo. This is the rst report of COF-based PDT excited by upconversion uorescence, providing the possibility of deep PDT.Corrole-based COFs406,461 have been successfully synthesized and have shown potential in PDT. Recently, Zhang et al…”

“…When the UCNP core was excited with a 980 nm laser, the emissions at 541 and 654 nm were absorbed by the TphDha COF shell to produce 1 O 2 , while the emission at 800 nm was not affected. Further study showed that when the thickness of the shell was 15 nm, the TphDha COF shell gave the best 1 406 TPAPC-COF adopts the staggered AB-stacking form with elliptical pores. The B-band absorption of TPAPC-COF is located at 399 nm, and the extended Q-band absorption is up to 2000 nm, which can be attributed to the huge p-electron delocalization system in the TPAPC-COF layer.…”

“…Here, we will introduce the different kinds of methods to make the bread: COF-based oncotherapy examples. Till now, COFs have been used as drug delivery carriers, 221,[396][397][398][399][400][401][402][403] phototherapy reagents, 163,216,223,261,[404][405][406][407][408][409][410] and combination therapy platforms 161,162,220,[411][412][413][414][415] for tumor therapeutics ( Table 5).…”

Recent Progress in Nanoscale Covalent Organic Frameworks for Cancer Diagnosis and Therapy

“…PDT, as a promising treatment method, has attracted considerable research interest [ 99 ], which has been applied in clinical cancer therapy. Gan et al [ 35 ] reported a 2D COF nanosheet with loaded photosensitizer indocyanine green (ICG), namely, ICG@COF-1@PDA, which was prepared by loading ICG in COF-1 nanosheet, and subsequently coated with polydopamine (PDA) (Fig.…”