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1. The luminescent and photophysical properties of covalent organic frameworks

   https://doi.org/10.1039/c9cs00807a  

   Haug, W. Karl; Moscarello, Erica M.; Wolfson, Eric R.; McGrier, Psaras L. (February 2020, Chemical Society Reviews)

   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. 

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2. Conductive Framework Materials for Chemiresistive Detection and Differentiation of Toxic Gases

   https://doi.org/10.1021/acs.accounts.4c00319  

   Benedetto, Georganna; Mirica, Katherine A (October 2024, Accounts of Chemical Research)

   Sensing complex gaseous mixtures and identifying their composition and concentration have the potential to achieve unprecedented improvements in environmental monitoring, medical diagnostics, industrial safety, and the food/agriculture industry. Electronically transduced chemical sensors capable of recognizing and differentiating specific target gases and transducing these chemical stimuli in a portable electronic device offer an opportunity for impact by bridging the utility of chemical information with global wireless connectivity. Among electronically transduced chemical sensors, chemiresistors stand out as particularly promising due to combined features of low-power requirements, room temperature operation, non-line-of-sight detection, high portability, and exceptional modularity. Relying on changes in resistance of a functional material triggered by variations in the surrounding chemical environment, these devices have achieved part-per-billion sensitivities of analytes by employing conductive polymers, graphene, carbon nanotubes (CNTs), metal oxides, metal nanoparticles, metal dichalcogenides, or MXenes as sensing materials. Despite these tremendous developments, the need for stable, selective, and sensitive chemiresistors demands continued innovation in material design in order to operate in complex mixtures with interferents as well as variations in humidity and temperature. To fill existing gaps in sensing capabilities, conductive metal−organic frameworks (MOFs) and covalent organic frameworks (COFs) have recently emerged as a promising class of materials for chemiresistive sensing. In contrast to previously reported chemiresistors, these materials offer at least three unique features for gas sensing applications: (i) bottom-up synthesis from molecularly precise precursors that allows for strategic control of material−analyte interactions, (ii) intrinsic conductivity that simultaneously facilitates charge transport and signal transduction under low power requirements, and (iii) high surface area that enables the accessibility of abundant active sites and decontamination of gas streams by coordinating to and, sometimes, detoxifying harmful analytes. Through an emphasis on molecular engineering of structure−property relationships in conductive MOFs and COFs, combined with strategic innovations in device integration strategies and device form factor (i.e., the physical dimensions and design of device components), our group has paved the way to demonstrating the multifunctional utility of these materials in the chemiresistive detection of gases and vapors. Backed by spectroscopic assessment of material−analyte interactions, we illustrated how molecular-level features lead to device performance in detection, filtration, and detoxification of gaseous analytes. By merging the bottom-up synthesis of these materials with device integration, we show the versatility and scalability of using these materials in low-power electronic sensing devices. Taken together, our achievements, combined with the progress spearheaded on this class of materials by other researchers, establish conductive MOFs and COFs as promising multifunctional materials for applications in electronically transduced, portable, low-power sensing devices. 

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3. Synthesis, Postsynthetic Modifications, and Applications of the First Quinoxaline-Based Covalent Organic Framework

   https://doi.org/https://doi.org/10.1021/acsami.1c08854  

   Valerie A. Kuehl, Phuoc H. (January 2021, ACS applied materials interfaces)

   We report a new synthetic protocol for preparing highly ordered two-dimensional nanoporous covalent organic frameworks (2D-COFs) based on a quinoxaline backbone. The quinoxaline framework represents a new type of COF that enables postsynthetic modification by placing two different chemical functionalities within the nanopores including layer-to-layer cross-linking. We also demonstrate that membranes fabricated using this new 2D-COF perform highly selective separations resulting in dramatic performance enhancement post cross-linking. 

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4. Covalent Organic Frameworks as Electrode Materials for Rechargeable Batteries

   https://doi.org/10.1055/s-0041-1723020  

   Wolfson, Eric R.; Moscarello, Erica M.; Haug, William K.; McGrier, Psaras L. (January 2021, Organic Materials)

   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. 

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5. Challenges in photocatalysis using covalent organic frameworks

   https://doi.org/10.1088/2515-7647/ad5777  

   Jiang, Shu-Yan; Senftle, Thomas P; Verduzco, Rafael (June 2024, Journal of Physics: Photonics)

   Abstract Photocatalysis is an attractive, energy-efficient technology for organic transformations, polymer synthesis, and degradation of environmental pollutants. There is a need for new photocatalysts stable in different media and that can be tailored for specific applications. Covalent organic frameworks (COF) are crystalline, nanoporous materials withπ-conjugated backbone monomers, representing versatile platforms as heterogeneous, metal-free photocatalysts. The backbone structure can be tailored to achieve desired photocatalytic properties, side-chains can mediate adsorption, and the nanoporous structure provides large surface area for molecular adsorption. While these properties make COFs attractive as photocatalysts, several fundamental questions remain regarding mechanisms for different photocatalytic transformations, reactant transport into porous COF structures, and both structural and chemical stability in various environments. In this perspective, we provide a brief overview of COF photocatalysts and identify challenges that should be addressed in future research seeking to employ COFs as photocatalysts. We close with an outlook and perspective on future research directions in the area of COF photocatalysts. 

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