MOFs@Top J：2022.04.10-2022.04.16

Metal–Organic Frameworks in Mixed-Matrix Membranes for High-Speed Visible-Light Communication
Journal of the American Chemical Society， Pub Date : 2022-04-12 ,

DOI: 10.1021/jacs.2c00483
Jian-Xin Wang, Yue Wang, Issatay Nadinov, Jun Yin, Luis Gutiérrez-Arzaluz, George Healing, Omar Alkhazragi, Youdong Cheng, Jiangtao Jia, Norah Alsadun, Vinayak S. Kale, Chun Hong Kang, Tien Khee Ng, Osama Shekhah, Husam N. Alshareef, Osman M. Bakr, Mohamed Eddaoudi, Boon S. Ooi, Omar F. Mohammed

Mixed-matrix membranes (MMMs) based on luminescent metal–organic frameworks (MOFs) and emissive polymers with the combination of their unique advantages have great potential in separation science, sensing, and light-harvesting applications. Here, we demonstrate MMMs for the field of high-speed visible-light communication (VLC) using a very efficient energy transfer strategy at the interface between a MOF and an emissive polymer. Our steady-state and ultrafast time-resolved experiments, supported by high-level density functional theory calculations, revealed that efficient and ultrafast energy transfer from the luminescent MOF to the luminescent polymer can be achieved. The resultant MMMs exhibited an excellent modulation bandwidth of around 80 MHz, which is higher than those of most well-established color-converting phosphors commonly used for optical wireless communication. Interestingly, we found that the efficient energy transfer further improved the light communication data rate from 132 Mb/s of the pure polymer to 215 Mb/s of MMMs. This finding not only showcases the promise of the MMMs for high-speed VLC but also highlights the importance of an efficient and ultrafast energy transfer strategy for the advancement of data rates of optical wireless communication.

https://pubs.acs.org/doi/abs/10.1021/jacs.2c00483

Covalent Organic Framework for Rechargeable Batteries: Mechanisms and Properties of Ionic Conduction

Advanced Energy Materials， Pub Date : 2022-04-10 , 

DOI: 10.1002/aenm.202200057
Yu Cao, Meidi Wang, Hongjian Wang, Chengyu Han, Fusheng Pan, Jie Sun

Ionic conduction plays a critical role in the process of electrode reactions and the charge transfer kinetics in a rechargeable battery. Covalent organic frameworks (COFs) have emerged as an exciting new class of ionic conductors, and have made great progress in terms of their application in rechargeable batteries. The unique features of COFs, such as well-defined directional channels, functional diversity, and structural robustness, endow COF-based conductors with a low ionic diffusion energy barrier and excellent temperature tolerance, which are much superior to the classic inorganic or polymer conductors. Here, a comprehensive analysis and summary of the unique ion-conducting behavior of COF-based conductors are presented, and the design principles for ion-conducting COFs are emphasized. Moreover, a systematic overview of the recent progress in the development of ion-conducting COFs serving as electrodes, separators, solid electrolytes, and artificial interphase materials for diverse battery applications, such as metal-ion batteries, lithium metal batteries, lithium–sulfur batteries, lithium–CO2 batteries, zinc–air batteries, etc., is proposed. This review is expected to provide theoretical guidance for design of novel kinds of ionic conductor bearing intrinsic framework structures and to boost further research enthusiasm for ion-conducting COFs in rechargeable batteries.

https://onlinelibrary.wiley.com/doi/full/10.1002/aenm.202200057

Synthesis of Metal-Free Chiral Covalent Organic Framework for Visible-Light-Mediated Enantioselective Photooxidation in Water
Journal of the American Chemical Society ， Pub Date : 2022-04-08 ,

DOI: 10.1021/jacs.2c01186
Xuan Kan, Jian-Cheng Wang, Zhi Chen, Jia-Qi Du, Jing-Lan Kan, Wen-Yan Li, Yu-Bin Dong

Although chiral covalent organic frameworks (CCOFs) presence grows in thermal asymmetric catalysis, their application in equally important asymmetric photocatalysis has yet to begin. Herein, we first report a propargylamine-linked and quaternary ammonium bromide decorated porphyrin-CCOF which can highly promote visible-light-driven enantioselective photooxidation of sulfides to sulfoxides in water and in air. This methodology has also been applied to the synthesis of (R)-modafinil, a wakefulness-promoting medication used for the treatment of excessive sleepiness. This research might open a new way for the application of CCOFs in asymmetric photocatalysis.

https://pubs.acs.org/doi/abs/10.1021/jacs.2c01186

Generation of Hierarchical Pores in Metal-Organic Frameworks by Introducing Rigid Modulator

CCS Chemistry Pub Date : 2022-04-08 , 

DOI: 10.31635/ccschem.022.202201974
Zhiwen Ai, Long Jiao, Jingxue Wang, Hai-Long Jiang

The fabrication of hierarchically porous metal-organic frameworks (HP-MOFs) that combine tunable mesopore sizes with high stability is highly desired while remaining a challenge. Herein, a facile and versatile “rigid modular-assisted defect formation” strategy has been developed to transform microporous MOFs into their corresponding HP-MOFs. By controlling the modulator dose and acid amount, the pore size and mesopore percentage can be finely regulated. Thanks to the hierarchical pores, the mass transfer of molecules with large sizes is significantly promoted. As a result, the representative HP-UiO-66-NH2-OTf, decorated with trifluoromethanesulfonate (OTf) group to enhance Lewis acidity, exhibits excellent activity and selectivity in tandem catalysis, far superior to the pristine UiO-66-NH2. This work provides a novel strategy to the general synthesis of stable HP-MOFs.

AIE based luminescent porous materials as cutting-edge tool for environmental monitoring: State of the art advances and perspectives

Coordination Chemistry Reviews， Pub Date : 2022-04-07 , DOI: 10.1016/j.ccr.2022.214539
Muhammad Asad, Muhammad Imran Anwar, Ansar Abbas, Ayesha Younas, Sameer Hussain, Ruixia Gao, Lin-Ke Li, M. Shahid, Shabnam Khan

Various research groups around the globe are focusing on the design and development of innovative luminescent systems, because of their multiple and unique features such as remarkable sensitivity, rapid signal response time, and ease of operation. In particular, aggregation-induced emission (AIE) based luminescent frameworks have emerged as potential candidates for sensing applications owing to the distinct emission property of AIE luminogens (AIEgens). Thus, numerous AIEgen-based porous materials like metal organic frameworks (MOFs), covalent organic frameworks (COFs), porous organic polymers (POPs), and metal organic cages (MOCs) have been established over the past decade for sensing applications with exceptional performances that surpass the conventional luminescent probes. This review provides systematic information on the fundamentals of AIE, the operating mechanism involved, and finally sheds light on recent advancements in AIE-based luminescent porous materials (MOFs, COFs, POPs, and MOCs) for potential sensing applications with special emphasis on environmental safety. The important detection parameters such as sensitivity, response time, selectivity, etc., of such AIE porous materials are highlighted for the detection of a variety of chemical compounds.

2D Covalent Organic Frameworks with cem Topology
Journal of the American Chemical Society， Pub Date : 2022-04-13 ,

DOI: 10.1021/jacs.2c01082
Xuan Wang, Xing Han, Cheng Cheng, Xing Kang, Yan Liu, Yong Cui

Affiliation  

A large number of covalent organic frameworks (COFs) with two-dimensional (2D) layered structures have been reported, but their network structures are restricted to only seven topologies (namely, hcb, hxl, kgm, sql, tth, bex, and kgd) because of the limited choice of building blocks. In this work, we illustrate how linking pseudo-fivefold symmetric 1,2,3,4,5-penta(4-formylphenyl)pyrrole with linear aromatic diamines through dynamic imine bonds produces three 2D porous COFs with an unprecedented cem topology, which represent the first examples of five-vertex semiregular Archimedean tessellations in COFs. The three 2D COFs are isostructural, and each adopts an eclipsed stacking structure with unidirectional hierarchical pores, in which the pyrrole unit is utilized as the five-vertex of network to form both square and triangular pores in a 33.42 sequence. With high thermal and chemical resistances, the COF-packed HPLC columns show excellent performance to provide separation of 10 different polycyclic aromatic hydrocarbons, a group of the most widespread organic environmental pollutants. The implementation of five-vertex Archimedean tessellations thus couriers a strategy to design COFs with new topologies and paves a new way to expand the inimitable properties of COF materials.

https://pubs.acs.org/doi/abs/10.1021/jacs.2c01082

Outstanding Charge Mobility by Band Transport in Two-Dimensional Semiconducting Covalent Organic Frameworks
Journal of the American Chemical Society， Pub Date : 2022-04-14 , DOI: 10.1021/jacs.2c02408
Shuai Fu, Enquan Jin, Hiroki Hanayama, Wenhao Zheng, Heng Zhang, Lucia Di Virgilio, Matthew A. Addicoat, Markus Mezger, Akimitsu Narita, Mischa Bonn, Klaus Müllen, Hai I. Wang

Two-dimensional covalent organic frameworks (2D COFs) represent a family of crystalline porous polymers with a long-range order and well-defined open nanochannels that hold great promise for electronics, catalysis, sensing, and energy storage. To date, the development of highly conductive 2D COFs has remained challenging due to the finite π-conjugation along the 2D lattice and charge localization at grain boundaries. Furthermore, the charge transport mechanism within the crystalline framework remains elusive. Here, time- and frequency-resolved terahertz spectroscopy reveals intrinsically Drude-type band transport of charge carriers in semiconducting 2D COF thin films condensed by 1,3,5-tris(4-aminophenyl)benzene (TPB) and 1,3,5-triformylbenzene (TFB). The TPB–TFB COF thin films demonstrate high photoconductivity with a long charge scattering time exceeding 70 fs at room temperature which resembles crystalline inorganic materials. This corresponds to a record charge carrier mobility of 165 ± 10 cm2 V–1 s–1, vastly outperforming that of the state-of-the-art conductive COFs. These results reveal TPB–TFB COF thin films as promising candidates for organic electronics and catalysis and provide insights into the rational design of highly crystalline porous materials for efficient and long-range charge transport.

https://pubs.acs.org/doi/abs/10.1021/jacs.2c02408

Construction of a two-dimensional artificial antioxidase for nanocatalytic rheumatoid arthritis treatment
Nature Communications， Pub Date : 2022-04-13 , 

DOI: 10.1038/s41467-022-29735-1
Bowen Yang, Heliang Yao, Jiacai Yang, Chang Chen, Jianlin Shi

Constructing nanomaterials mimicking the coordination environments of natural enzymes may achieve biomimetic catalysis. Here we construct a two-dimensional (2D) metal-organic framework (MOF) nanosheet catalyst as an artificial antioxidase for nanocatalytic rheumatoid arthritis treatment. The 2D MOF periodically assembles numbers of manganese porphyrin molecules, which has a metal coordination geometry analogous to those of two typical antioxidases, human mitochondrial manganese superoxide dismutase (Mn-SOD) and human erythrocyte catalase. The zinc atoms of the 2D MOF regulate the metal-centered redox potential of coordinated manganese porphyrin ligand, endowing the nanosheet with both SOD- and catalase-like activities. Cellular experiments show unique anti-inflammatory and pro-biomineralization performances of the 2D MOF, while in vivo animal model further demonstrates its desirable antiarthritic efficacy. It is expected that such a nanocatalytic antioxidation concept may provide feasible approaches to future anti-inflammatory treatments.

https://www.nature.com/articles/s41467-022-29735-1