Three dimensional nanoscale analysis reveals aperiodic mesopores in a covalent organic framework and conjugated microporous polymer

Stoppiello, Craig T.; Isla, Helena; Martínez‐Abadía, Marta; Fay, Michael W.; Parmenter, Christopher; Roe, Martin; Lerma‐Berlanga, Belén; Martí‐Gastaldo, Carlos; Mateo‐Alonso, Aurelio; Khlobystov, Andrei N.

doi:10.1039/c8nr10086a

Cited by 20 publications

(8 citation statements)

References 31 publications

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“…In some particular areas of [30]KL-FAN,s eemingly crystalline regions can be observed (Figure 2i)w ith some periodic features being attributed to the stacking arrangements of the individual layers.T he unexpected mesopores within the structure (Figure 2i)a re likely to be caused by the presence of solvent molecules during the formation of the FANl attice and terminated by unreacted carbonyl groups due to incomplete condensation, as we previously demonstrated for aconjugated microporous polymer. [20] Theo ptical properties of [30]KL-FAN and [90]KL-FAN were studied by UV/Vis-NIR spectroscopy (Figure 4a,b). Thin films were obtained by drop-casting dispersions of [30]KL-FAN and [90]KL-FAN in trifluoroacetic acid (TFA) directly onto ag lass slide,w hich allowed estimating the optical band gap using Taucsm ethod (inset Figure 4a,b).…”

Section: Resultsmentioning

confidence: 99%

An Expanded 2D Fused Aromatic Network with 90‐Ring Hexagons

et al. 2021

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Two-dimensional fused aromatic networks (2D FANs) have emerged as ah ighly versatile alternative to holey graphene.T he synthesis of 2D FANs with increasingly larger lattice dimensions will enable new application perspectives.H owever,t he synthesis of larger analogues is mostly limited by lack of appropriate monomers and methods.Herein, we describe the synthesis,characterisation and properties of an expanded 2D FANw ith 90-ring hexagons,w hiche xceed the largest 2D FANl attices reported to date.

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Section: Resultsmentioning

confidence: 99%

An Expanded 2D Fused Aromatic Network with 90‐Ring Hexagons

et al. 2021

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“…This interpretation is also in agreement with the simulations on a free-standing Marta-COF-1 layer that shows larger diameters than those in a condensed phase ( Figure S12). TEM tomography, a process of sequential imaging and tilting of a particle has previously reported to be an excellent method to elucidate the internal structure of COFs and less crystalline conjugated microporous polymers, 41 however this technique is limited by the stability of the samples. Thanks to the high stability of Marta-COF-1, it was possible performing HR-TEM tilt experiments of individual crystallites over 70° (Figures 4g and S14).…”

Section: Resultsmentioning

confidence: 99%

A Wavy Two-Dimensional Covalent Organic Framework from Core-Twisted Polycyclic Aromatic Hydrocarbons

et al. 2019

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A high degree of crystallinity is an essential aspect in two-dimensional covalent organic frameworks, as many properties depend strongly on the structural arrangement of the different layers and their constituents. We introduce herein a new design strategy based on core-twisted polycyclic aromatic hydrocarbon as rigid nodes that give rise to a two-dimensional covalent organic framework with a wavy honeycomb (chair-like) lattice. The concave-convex self-complementarity of the wavy two-dimensional lattice guides the stacking of framework layers into a highly stable and ordered covalent organic framework that allows a full 3D analysis by transmission electron microscopy revealing its chair-like honeycomb facets and aligned mesoporous channels. Remarkably, the waviness of the framework does not disrupt the interlayer π-π stacking that shows charge transporting properties similar to those of planar covalent organic frameworks. The implementation of core-twisted aromatics as building blocks for covalent organic frameworks brings new possibilities in the design of highly ordered organic materials.

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“…For MOF vacancies by structural modulators or fragmented linker strategy, NMR spectroscopy after MOF digestion is a powerful tool to determine the ratio between the linkers and modulators/fragments, and thus amount of the defects can be concluded. [195][196][197][198] However, the analysis could only track the organic components in the MOFs, and thus the information on cluster vacancies is not available. When NMR is combined with TGA and EA, an accurate structural formula showing defects with missing organic components (missing linker or missing functionality) and/or missing inorganic components (missing cluster or missing metal) could be obtained.…”

Section: Vacancy Identification and Quantificationmentioning

confidence: 99%

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

Pang

Yang

2022

Small Structures

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Vacancies in crystalline materials are missing single atoms and missing clusters of atoms in the ordered lattice. In reticular structures such as metal−organic frameworks (MOFs), vacancy can exist in the form of organic linker vacancy, inorganic cluster vacancy, and macroscopic vacancy. In last decade, extensive researches have been developed in exploring the formation, arrangement, and functions of vacancies in MOFs. In this review, an overview of progress in introducing structural vacancies into MOFs either by de novo synthesis or by postsynthetic modification is provided. Different spatial arrangements of vacancies (random, site‐selective, and correlated/ordered) are also highlighted, with an emphasis on new synthetic strategies and mechanisms, and advanced characterization methods needed to control vacancies in a sophisticated manner. Furthermore, enhanced gas adsorption, precise framework grafting, and efficient molecular conversion empowered by vacancies in MOFs are summarized. Future opportunities in this field are envisioned by considering vacancies as a new kind of constituents to reshape the MOF backbone and pores for higher structural complexities and tailored functions.

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Three dimensional nanoscale analysis reveals aperiodic mesopores in a covalent organic framework and conjugated microporous polymer

Abstract: Stable aperiodic channels of 20–50 nm in COF-5 and Aza-CMP shed light on polymer particle growth.

Cited by 20 publications

References 31 publications

An Expanded 2D Fused Aromatic Network with 90‐Ring Hexagons

An Expanded 2D Fused Aromatic Network with 90‐Ring Hexagons

A Wavy Two-Dimensional Covalent Organic Framework from Core-Twisted Polycyclic Aromatic Hydrocarbons

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

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