Gas-Triggered Gate-Opening in a Flexible Three-Dimensional Covalent Organic Framework

Liu, Xiaoling; Wang, Zhifang; Zhang, Ya; Yang, Na; Gui, Bo; Sun, Junliang; Wang, Cheng

doi:10.1021/jacs.4c01331

Cited by 4 publications

(2 citation statements)

References 55 publications

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“…The burgeoning field of materials science is continuously unveiling novel structures with unprecedented properties, and among these, covalent organic frameworks (COFs) stand out for their potential in a myriad of applications [ 1 , 2 , 3 , 4 , 5 ]. Extending the versatility of COFs, zwitterionic covalent organic frameworks (Z-COFs) represent a fascinating subclass that incorporates both positively and negatively charged functional groups within a single, well-defined structure.…”

Section: Introductionmentioning

confidence: 99%

Interlayer Interactions and Macroscopic Property Calculations of Squaric-Acid-Linked Zwitterionic Covalent Organic Frameworks: Structures, Photocatalytic Carrier Transport, and a DFT Study

Yan,

Zhang

2024

Molecules

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Squaric-acid-linked zwitterionic covalent organic frameworks (Z-COFs), assembled through interlayer interactions, are emerging as potential materials in the field of photocatalysis. However, the study of their interlayer interactions has been largely overlooked. To address this, this work systematically calculated interlayer interactions via density functional theory (DFT) and analyzed the differences in interlayer interactions of different structures of Z-COFs through interlayer slippage, planarity, and an independent gradient model based on the Hirshfeld partition (IGMH). Furthermore, it revealed the relationship between the interactions and the macroscopic photocatalytic carrier transport performance of the material. The results indicated that both preventing interlayer slippage and enhancing planarity can enhance the interlayer interactions of Z-COFs, thereby improving their macroscopic carrier transport performance in photocatalysis.

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Section: Introductionmentioning

confidence: 99%

Interlayer Interactions and Macroscopic Property Calculations of Squaric-Acid-Linked Zwitterionic Covalent Organic Frameworks: Structures, Photocatalytic Carrier Transport, and a DFT Study

Yan,

Zhang

2024

Molecules

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“…Covalent organic frameworks (COFs) have emerged as a new kind of porous polymers, which allow the assembly of various organic building blocks through strong covalent bonds at atomic precision. − Owing to their specific construction modes, most COFs have exhibited multiple advantages, such as high crystallinity, flexible structures, and strong robustness, which endow these materials with tremendous application foreground in gas adsorption, − heterogeneous catalysis, − optoelectronics, − sensing, − and energy storage. − Although a large number of two-dimensional (2D) COFs with triangular, tetragonal, and hexagonal pores have been developed through the rational combination of building blocks with different symmetries, − the construction of COFs with pentagonal pores remains a great challenge as it conflicts with the principle of plane geometry. − …”

mentioning

confidence: 99%

Two-Dimensional Covalent Organic Frameworks with Pentagonal Pores

Wen,

Xu,

Feng

et al. 2024

J. Am. Chem. Soc.

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The pore shapes of two-dimensional covalent organic frameworks (2D COFs) significantly limit their practical applications in separation and catalysis. Although various 2D COFs with polygonal pores have been well developed, constructing COFs with pentagonal pores remains an enormous challenge. In this work, we developed one kind of pentagonal COFs with the mcm topological structure for the first time, through the rational combination of C 4 and C 2 symmetric building blocks. The resulting pentagonal COFs exhibit high crystallinity, excellent porosity, and strong robustness. Moreover, the inbuilt porphyrin units render these COFs as efficient electrocatalytic catalysts toward oxygen reduction reaction with a half-wave potential of up to 0.81 V, which ranks as one of the highest values among COFs-based electrocatalysts. This work not only verified the possibility of constructing 2D COFs with pentagonal pores but also developed a strategy for the construction of functional 2D COFs for interesting applications.

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Single-Crystal Dynamic Covalent Organic Frameworks for Adaptive Guest Alignments

Liu,

Wei,

Zeng

et al. 2024

J. Am. Chem. Soc.

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Dynamic 3D covalent organic frameworks (COFs) have shown a concerted structural transformation upon adaptive guest inclusion. However, the origin of the conformational mobility and the host−guest adaptivity remain conjecture of the pedal motions of revolving imine linkages, often without considering the steric hindrance from the interwoven frameworks. Here, we present atomic-level observation of the rotational and translational dynamics in single-crystal COF-300 upon adaptive guest inclusion of various organic molecules, featuring multiple rotamers of covalent linkages and switchable interframework noncovalent interactions. Specifically, we developed a diffusion gradient transimination protocol to facilitate the growth of COF single crystals, enabling a high-resolution X-ray diffraction structural analysis. We uncovered metastable and low-symmetry intermediate phases from contracted to expanded phases during structural evolution. We identified torsion angles in the terephthalaldehyde diimine motifs that switch from anti-periplanar to syn-periplanar/anticlinal conformations. Moreover, the rotational dynamics of the imine linkage were concurrent with the translational dynamics of tetraphenylmethane units, which tend to form the translational quadruple phenyl embrace. Such conformational mobility allows the frameworks to adapt to various guest molecules, such as alcohols, esters, phenols, and diols, featuring double linear, herringbone, zigzag chains, triple helix, and tubular alignments. Quantitative energy analyses revealed that such dynamic structure transformations are not arbitrary but follow specific pathways that resemble protein folding. The work is paving the way to developing robust, dynamic, and crystalline molecular sponges for studying the condensed structure of liquids without the need for further crystallization.

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Gas-Triggered Gate-Opening in a Flexible Three-Dimensional Covalent Organic Framework

Cited by 4 publications

References 55 publications

Interlayer Interactions and Macroscopic Property Calculations of Squaric-Acid-Linked Zwitterionic Covalent Organic Frameworks: Structures, Photocatalytic Carrier Transport, and a DFT Study

Interlayer Interactions and Macroscopic Property Calculations of Squaric-Acid-Linked Zwitterionic Covalent Organic Frameworks: Structures, Photocatalytic Carrier Transport, and a DFT Study

Two-Dimensional Covalent Organic Frameworks with Pentagonal Pores

Single-Crystal Dynamic Covalent Organic Frameworks for Adaptive Guest Alignments

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