Self‐Assembled, Fluorine‐Rich Porous Organic Polymers: A Class of Mechanically Stiff and Hydrophobic Materials

Mukherjee, Soumya; Zeng, Zhixin; Shirolkar, Mandar M.; Samanta, Partha; Chaudhari, Abhijeet K.; Tan, Jin‐Chong; Ghosh, Sujit K.

doi:10.1002/chem.201802200

Cited by 8 publications

(6 citation statements)

References 81 publications

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“…Recent investigations to measure the Young’s moduli of 2D COFs found values ranging from ∼10 MPa to 267 GPa, which spans over 4 orders of magnitude. − It is still unclear whether such large variations can be entirely attributed to the different molecular structures of the COFs under study or are caused by the potential impact of factors such as the presence of structural defects and grain boundaries in the COF films. At this point of time, it remains a great challenge indeed to obtain few-layer, large-area 2D COFs, while routinely fabricated 2D COF films are often composed of aggregated small crystals, − which complicate the characterization of their intrinsic mechanical properties.…”

Section: Introductionmentioning

confidence: 99%

Impact of Structural Defects on the Elastic Properties of Two-Dimensional Covalent Organic Frameworks (2D COFs) under Tensile Stress

Brédas

2021

Chem. Mater.

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Two-dimensional covalent organic frameworks (2D COFs) represent an emerging class of permanently porous, lightweight materials. While their mechanical properties represent a fundamental intrinsic feature most relevant for their applications, they remain poorly understood. This is exemplified by the fact that there exists a large variation in previously reported Young’s moduli. Also, a large number of structural defects can be present within the 2D COF films, whose impact on the mechanical properties needs to be addressed. Here, based on an efficient computational protocol to evaluate the Young’s moduli and Poisson’s ratios of 2D COFs from molecular dynamics simulations, we investigate the mechanical properties, under tensile stress, of representative (honeycomb-kagome) boronate ester- and imine-linked 2D COFs, i.e., COF-5 and TAPB-PDA COF. In both systems, the Young’s moduli are found to be dependent on the stretching direction and range from 4 to 24 GPa. A large Poisson’s ratio of 0.9–1.1 is found, which suggests that 2D COFs have a large contraction in the transverse direction when stretched. These results point to 2D COFs as anisotropic elastic materials. Importantly, the presence of structural defects is found to significantly impact the mechanical properties of 2D COFs. For instance, the presence of 3% vacancies can lead to a ∼50% decrease in Young’s modulus. Our work provides a comprehensive understanding of the elastic properties of representative 2D COFs, a useful stepping stone when considering these systems for a variety of applications.

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Section: Introductionmentioning

confidence: 99%

Impact of Structural Defects on the Elastic Properties of Two-Dimensional Covalent Organic Frameworks (2D COFs) under Tensile Stress

Brédas

2021

Chem. Mater.

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“…44 Studies of mechanical stiffness of CTFs substituted with trifluoromethyl groups revealed behavior similar to glass polymers and zeolitic imidazolate frameworks. 45 Qi and coworkers have prepared fluorinated POPs (Figure 2, bottom right) by Pd-catalyzed C-H activation of 1,2,4,5-tetrafluorobenzene and its subsequent coupling with trigonal and tetrahedral aryl bromides. 46 Using ironporphyrin as a coupling partner, a series of fluorinated POPs was prepared with Brunauer-Emmett-Teller (BET) surface areas ranging between 670 and 840 m 2 g -1 .…”

Section: Covalent Organic Framework and Porous Organic Polymersmentioning

confidence: 99%

Fluorinated Organic Porous Materials

Zhang

Miljanić

2019

Organic Materials

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Fluorine is in many aspects unique among the elements, and its incorporation into organic molecules can dramatically change their physical and chemical properties. This minireview will survey the existing classes of fluorinated porous materials, with a particular focus on all-organic porous materials. We will highlight our work on the preparation and study of metal–organic frameworks and porous molecular crystals derived from extensively fluorinated rigid aromatic pyrazoles and tetrazoles. Where possible, comparisons between fluorinated and nonfluorinated materials will be made.

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“…Several POPs with polar segments were prepared and tested in reversible water vapour capture from the air [ 19 , 20 ]. On the contrary, highly hydrophobic fluorine-rich POPs were also prepared [ 21 , 22 ] and applied to capture the vapour of non-polar hydrocarbons and fluorinated compounds. Application-interesting POPs with ionic [ 20 , 23 ], luminescent [ 24 ], chiral [ 25 , 26 ], and other groups [ 27 , 28 ] were also reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible H2O and CO2 Capture and Construction of Porous Chiral Networks

et al. 2023

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Two series of hyper-cross-linked microporous polyacetylene networks containing either -[CH=C(CH=O)]- or -[CH=C(CH2OH)]- monomeric units are reported. Networks are prepared by chain-growth copolymerization of acetal-protected propargyl aldehyde and acetal-protected propargyl alcohol with a 1,3,5-triethynylbenzene cross-linker followed by hydrolytic deprotection/detemplating. Deprotection not only liberates reactive CH=O and CH2OH groups in the networks but also modifies the texture of the networks towards higher microporosity and higher specific surface area. The final networks with CH=O and CH2OH groups attached directly to the polyene main chains of the networks have a specific surface area from 400 to 800 m2/g and contain functional groups in a high amount, up to 9.6 mmol/g. The CH=O and CH2OH groups in the networks serve as active centres for the reversible capture of CO2 and water vapour. The water vapour capture capacities of the networks (up to 445 mg/g at 297 K) are among the highest values reported for porous polymers, making these materials promising for cyclic water harvesting from the air. Covalent modification of the networks with (R)-(+)-3-aminopyrrolidine and (S)-(+)-2-methylbutyric acid enables the preparation of porous chiral networks and shows networks with CH=O and CH2OH groups as reactive supports suitable for the anchoring of various functional molecules.

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Self‐Assembled, Fluorine‐Rich Porous Organic Polymers: A Class of Mechanically Stiff and Hydrophobic Materials

Cited by 8 publications

References 81 publications

Impact of Structural Defects on the Elastic Properties of Two-Dimensional Covalent Organic Frameworks (2D COFs) under Tensile Stress

Impact of Structural Defects on the Elastic Properties of Two-Dimensional Covalent Organic Frameworks (2D COFs) under Tensile Stress

Fluorinated Organic Porous Materials

Combining Polymerization and Templating toward Hyper-Cross-Linked Poly(propargyl aldehyde)s and Poly(propargyl alcohol)s for Reversible H2O and CO2 Capture and Construction of Porous Chiral Networks

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