Expanding the horizons of covalent organic frameworks: sub-stoichiometric synthesis as an emerging toolkit for functional COFs

Vijayakumar, Samiyappan; Ajayaghosh, Ayyappanpillai; Shankar, Sreejith

doi:10.1039/d3ta05715a

Cited by 3 publications

(1 citation statement)

References 180 publications

(268 reference statements)

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“…Next, we intended to exclude sub-stoichiometric structures, as these can lead to unexpected unit cells and can appear under specific synthesis conditions or when competing interactions are at play in the structure formation. 4,37,38 When comparing the IR spectra of the 4A2E-linker molecules and the 4A2E-PDA-COF (Figure S 6), the strong band corresponding to the C=O stretching of the aldehyde at 1681 cm -1 disappears for the formed 4A2E-PDA-COF, while the C=O stretch vibration of the methyl ester group only shifts slightly from 1715 cm -1 to 1733 cm -1 for the linker and the COF, respectively. At the same time a vibration at 1612 cm -1 appears that can be assigned to the imine C=N stretch vibration.…”

Section: Resultsmentioning

confidence: 99%

Enhancing Structural Control in Covalent Organic Frameworks through Steric Interaction-Driven Linker Design

Winter,

Hamdi,

Eichhöfer

et al. 2023

Preprint

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Covalent Organic Frameworks (COFs) exhibiting kagome (kgm) structures are promising crystalline porous materials with two distinct pores. However, the challenge arises from the potential formation of the polymorphic square-lattice (sql) structure, which is undesired in some cases. To this, we introduce a novel linker design strategy featuring bulky functional groups, enforcing the preferred kgm structure, while hindering sql network formation. Implementing this design, we synthesized a terphenyl core-based tetraaldehyde linker (4A2E) incorporating a bulky methoxycarbonyl-terminated phenyl group. By varying the diamine linker lengths, using phenylenediamine (PDA) and benzidine (Bz), the steric interaction was tuned leading to the formation of different topologies. Structural analysis revealed the formation of a kgm network formation with an unusual ABC stacking for the 4A2E-PDA-COF with the short PDA linker, in contrast to the sql network in 4A2E-Bz-COF with the longer benzidine. This steric interaction-driven design enhances control over COF structures, expanding the design toolbox, but also provides valuable insights into network formation and polymorphism.

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Section: Resultsmentioning

confidence: 99%

Enhancing Structural Control in Covalent Organic Frameworks through Steric Interaction-Driven Linker Design

Winter,

Hamdi,

Eichhöfer

et al. 2023

Preprint

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Unveiling the Potential of Covalent Organic Frameworks for Energy Storage: Developments, Challenges, and Future Prospects

Dubey,

Shrivastav,

Boruah

et al. 2024

Advanced Energy Materials

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Covalent organic frameworks (COFs) are porous structures emerging as promising electrode materials due to their high structural diversity, controlled and wide pore network, and amenability to chemical modifications. COFs are solely composed of periodically arranged organic molecules, resulting in lightweight materials. Their inherent properties, such as extended surface area and diverse framework topologies, along with their high proclivity to chemical modification, have positioned COFs as sophisticated materials in the realm of electrochemical energy storage (EES). The modular structure of COFs facilitates the integration of key functions such as redox‐active moieties, fast charge diffusion channels, composite formation with conductive counterparts, and highly porous network for accommodating charged energy carriers, which can significantly enhance their electrochemical performance. However, ascribing intricate porosity and redox‐active functionalities to a single COF structure, while maintaining long‐term electrochemical stability, is challenging. Efforts to overcome these hurdles embrace strategies such as the implementation of reversible linkages for structural flexibility, stimuli‐responsive functionalities, and incorporating chemical groups to promote the formation of COF heterostructures. This review focuses on the recent progress of COFs in EES devices, such as batteries and supercapacitors, through a meticulous exploration of the latest strategies aimed at optimizing COFs as advanced electrodes in future EES technologies.

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Enhancing structural control in covalent organic frameworks through steric interaction-driven linker design

Winter,

Hamdi,

Eichhöfer

et al. 2024

Chem. Sci.

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Expanding the horizons of covalent organic frameworks: sub-stoichiometric synthesis as an emerging toolkit for functional COFs

Abstract: Covalent Organic Frameworks (COFs) are a class of porous materials generated from organic molecules resulting in two-dimensional (2D) or three-dimensional (3D) networks. Multifunctional molecules with defined symmetry react to give...

Cited by 3 publications

References 180 publications

Enhancing Structural Control in Covalent Organic Frameworks through Steric Interaction-Driven Linker Design

Enhancing Structural Control in Covalent Organic Frameworks through Steric Interaction-Driven Linker Design

Unveiling the Potential of Covalent Organic Frameworks for Energy Storage: Developments, Challenges, and Future Prospects

Enhancing structural control in covalent organic frameworks through steric interaction-driven linker design

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