The first synthesis and comprehensive characterization of two vinyl tetrazine‐linked covalent organic frameworks (COF), TA‐COF‐1 and TA‐COF‐2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2g−1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light‐driven applications. These advantages enable TA‐COFs to act as reusable metal‐free photocatalysts in the arylboronic acids oxidation and light‐induced coupling of benzylamines. In addition, these TA‐COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HCl solution, HCl vapor, and NH3vapor. Further, the TA‐COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA‐COFs can also degrade 5‐nitro‐1,2,4‐triazol‐3‐one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight‐driven photocatalytic process; thus, revealing dual functionality of the protonated TA‐COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF‐based materials, facilitating advances in catalysis, sensing, and other related fields.
- Award ID(s):
- 1706025
- NSF-PAR ID:
- 10171308
- Date Published:
- Journal Name:
- Chemical Society Reviews
- Volume:
- 49
- Issue:
- 3
- ISSN:
- 0306-0012
- Page Range / eLocation ID:
- 708 to 735
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
null (Ed.)Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers that have attracted significant attention due to their tunable properties and structural robustness. As a result, COFs with luminescent properties are of great interest for fields such as chemical sensing, solid-state light emitters, photocatalysis, and optoelectronics. However, the bottom-up synthesis of luminescent COF systems remains a challenge in the field due to an abundance of competing non-radiative pathways, including phenomena such as aggregate caused quenching (ACQ). To overcome these obstacles, there has been a burgeoning investigation into the luminescent and photophysical properties of COFs. This review will highlight methods used to fabricate luminescent COFs and discuss the factors that are critical for their production. A collection of known luminescent COF systems will be featured. In addition, the ability to utilize the photophysical properties of COFs for applications related to photocatalysis, solid-state light emitters, and chemical sensing will be addressed. An outlook will address the current progress and remaining challenges facing the field to ultimately expand the scope of their applications.more » « less
-
Abstract Woven covalent organic frameworks (COF) possess entangled 3D frameworks. The metallated version of these structures contains spatially isolated Cu(I) centers and promising optoelectronic properties because of metal‐to‐ligand charge transfer (MLCT). However, despite their potential, woven COFs have not yet been investigated as photocatalysts. In this study, a new woven COF, Cu‐PhenBDA‐COF, functionalized with diacetylene bonds is developed. Cu‐PhenBDA‐COF is fully characterized, and the optoelectronic and photocatalytic properties are compared to previously reported Cu‐COF‐505. The diacetylene bonds of the linker positively impact the optoelectronic properties of Cu‐PhenBDA‐COF and result in a narrower bandgap and better charge separation efficiency. When the Cu(I) center is removed from both woven COFs, the absorption edge is blueshifted, resulting in a wider bandgap, and there is a considerable decrease in the charge separation efficiency, underscoring the pivotal role of MLCT. This trend is reflected in the photocatalytic activity of the woven COFs toward the degradation of sulfamethoxazole in water, where the highest reaction rate constant (
k app) is recorded for the metallated diacetylene functionalized woven COF, Cu‐PhenBDA‐COF. -
Abstract Emissive covalent organic frameworks (COFs) have recently emerged as next‐generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so‐called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well‐defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.8%) substoichiometric 2D‐COF (
COF‐SMU‐1 ) featuring free uncondensed aldehyde groups is reported. In particular,COF‐SMU‐1 features a dual‐pore architecture with an overallbex net topology, tunable emission in various organic solvents, and distinct colorimetric changes in the presence of water. To gain further insights into its photoluminescence properties, the charge transfer, excimer emission, and excited state exciton dynamics ofCOF‐SMU‐1 are investigated using femtosecond transient absorption spectroscopy in different organic solvents. Additionally, highly enhanced atmospheric water‐harvesting properties ofCOF‐SMU‐1 are revealed using FT‐IR and water sorption studies.The findings will not only lead to in‐depth understanding of structure–property relationships in emissive COFs but also open new opportunities for designing COFs for potential applications in solid‐state lighting and water harvesting. -
null (Ed.)Covalent organic frameworks (COFs) are an advanced class of crystalline porous polymers that have garnered significant interest due to their tunable properties and robust molecular architectures. As a result, COFs with energy-storage properties are of particular interest to the field of rechargeable battery electrode materials. However, investigation into COFs as candidates for energy-storage materials is still in its infancy. This review will highlight methods used to fabricate COFs used as electrode materials and discuss the factors that prove critical for their production. A collection of known COF-based energy-storage systems will be featured. In addition, the ability to utilize the storage properties of COFs for systems beyond traditional Li-ion batteries will be addressed. An outlook will address the current progress and remaining challenges facing the field to ultimately expand the scope of their applications.more » « less