Developing synthetic methodology to crystallize extended covalent structures has been an important pursuit of reticular chemistry. Here, we report a homogeneous synthetic route for imine covalent organic frameworks (COFs) where crystallites emerge from clear solutions without forming amorphous polyimine precipitates. The key feature of this route is the utilization of tert-butyloxycarbonyl group protected amine building blocks, which are deprotected in situ and gradually nucleate the crystalline framework. We demonstrate the utility of this approach by crystallizing a woven covalent organic framework (COF-112), in which covalent organic threads are interlaced to form a three-dimensional woven framework. The homogeneous imine COF synthesis also enabled the control of nucleation and crystal growth leading to uniform nanocrystals, through microwave-assisted reactions, and facile preparation of oriented thin films.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.7b07457 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Covalent Organic Frameworks with Carbon-centered Radical Sites for Promoting the 4e- Oxygen Reduction Reaction.
Angew Chem Int Ed Engl
January 2025
Institute of Materials Research and Engineering, Sensor and Flexible Electronics, 2 Fusionopolis Way, 138634, SINGAPORE.
Radical covalent organic frameworks (RCOFs) have demonstrated significant potential in redox catalysis and energy conversion applications. However, the synthesis of stable RCOFs with well-defined neutral carbon radical centers is challenging due to the inherent radical instability, limited synthetic methods and characterization difficulties. Building upon the understanding of stable carbon radicals and structural modulations for preparing crystalline COFs, herein we report the synthesis of a crystalline carbon-centered RCOF through a facile post-oxidation process.
View Article and Find Full Text PDFHypoxia-Responsive Covalent Organic Framework Nanoplatform for Breast-Cancer-Targeted Cocktail Immunotherapy via Triple Therapeutic Switch Mechanisms.
Small
January 2025
School of Pharmacy, Southwest Medical University, Luzhou, Sichuan, 646000, China.
Covalent organic frameworks (COFs), known for their exceptional in situ encapsulation and precise release capabilities, are emerging as pioneering drug delivery systems. This study introduces a hypoxia-responsive COF designed to encapsulate the chemotherapy drug gambogic acid (GA) in situ. Bimetallic gold-palladium islands were grown on UiO-66-NH (UiO) to form UiO@Au-Pd (UAPi), which were encapsulated with GA through COF membrane formation, resulting in a core-shell structure (UAPiGC).
View Article and Find Full Text PDFRemarkable increase in electrochemiluminescence of isomeric bipyridine-based covalent organic frameworks via regulating the direction of imine linkage for sensing application.
J Colloid Interface Sci
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China. Electronic address:
Covalent organic frameworks (COFs) with highly ordered structures and predictable optoelectronic properties provide an ideal platform to investigate the electrochemiluminescence (ECL) performance based on organic materials by atomically varying the molecular construction. Herein, the effect of imine-bond orientation on the ECL performance of COFs is investigated. We report two COFs (NC-COF and CN-COF) with different orientations of imine bonds using pyrene donor units (D) and bipyridine acceptor motifs (A) monomers.
View Article and Find Full Text PDFTuning the interlayer stacking of a vinylene-linked covalent organic framework for enhancing sacrificial agent-free hydrogen peroxide photoproduction.
Chem Sci
January 2025
Hunan Key Laboratory of Micro & Nano Materials Interface Science, College of Chemistry and Chemical Engineering, Central South University Changsha 410083 P. R. China
The layer-stacking mode of a two-dimensional (2D) material plays a dominant role either in its topology or properties, but remains challenging to control. Herein, we developed alkali-metal ion-regulating synthetic control on the stacking structure of a vinylene-linked covalent triazine framework (termed spc-CTF) for improving hydrogen peroxide (HO) photoproduction. Upon the catalysis of EtONa in Knoevenagel polycondensation, a typical eclipsed stacking mode (spc-CTF-4@AA) was built, while a staggered one (spc-CTF-4@AB) was constructed using LiOH.
View Article and Find Full Text PDFRing-in-Ring Assembly Facilitates the Synthesis of a [12]Cycloparaphenylene ABC-Type [3]Catenane.
Angew Chem Int Ed Engl
January 2025
Henan University, Colleg of Chemistry and Molecular Sciences, Jingmin, 475004, Kaifeng, CHINA.
Cycloparaphenylenes (CPPs) represent a significant challenge for the synthesis of mechanically interlocked architectures, because they lack heteroatoms, which precludes traditional active and passive template methods. To circumvent this problem and explore the fundamental and functional properties of CPP rotaxanes and catenanes, researches have resorted to unusual non-covalent and even to labor-intensive covalent template approaches. Herein, we report a ring-in-ring non-covalent template strategy that makes use of the surprisingly strong non-covalent inclusion of crown ethers into suitably sized CPPs.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!