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Controlled growth of imine-linked two-dimensional covalent organic framework nanoparticles.

ABSTRACT: Covalent organic frameworks (COFs) consist of monomers arranged in predictable structures with emergent properties. However, improved crystallinity, porosity, and solution processability remain major challenges. To this end, colloidal COF nanoparticles are useful for mechanistic studies of nucleation and growth and enable advanced spectroscopy and solution processing of thin films. Here we present a general approach to synthesize imine-linked 2D COF nanoparticles and control their size by favoring imine polymerization while preventing the nucleation of new particles. The method yields uniform, crystalline, and high-surface-area particles and is applicable to several imine-linked COFs. In situ X-ray scattering experiments reveal the nucleation of amorphous polymers, which crystallize via imine exchange processes during and after particle growth, consistent with previous mechanistic studies of imine-linked COF powders. The separation of particle formation and growth processes offers control of particle size and may enable further improvements in crystallinity in the future.

SUBMITTER: Li RL

PROVIDER: S-EPMC6446964 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Controlled growth of imine-linked two-dimensional covalent organic framework nanoparticles.

Li Rebecca L RL Flanders Nathan C NC Evans Austin M AM Ji Woojung W Castano Ioannina I Chen Lin X LX Gianneschi Nathan C NC Dichtel William R WR

Chemical science 20190221 13

Covalent organic frameworks (COFs) consist of monomers arranged in predictable structures with emergent properties. However, improved crystallinity, porosity, and solution processability remain major challenges. To this end, colloidal COF nanoparticles are useful for mechanistic studies of nucleation and growth and enable advanced spectroscopy and solution processing of thin films. Here we present a general approach to synthesize imine-linked 2D COF nanoparticles and control their size by favori ...[more]

PMID: 30996969

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Project description:Mechanistic understanding into the formation and growth of imine-linked two-dimensional (2D) covalent organic frameworks (COFs) is needed to improve their materials quality and access larger crystallite sizes, both of which limit the promise of 2D COFs and 2D polymerization techniques. Here we report a previously unknown temperature-dependent depolymerization of colloidal 2D imine-linked COFs, which offers a new means to improve their crystallinity. 2D COF colloids form at room temperature but then depolymerize when their reaction mixtures are heated to 90 °C. As the solutions are cooled back to room temperature, the 2D COFs repolymerize and crystallize with improved crystallinity and porosity, as characterized by X-ray diffraction, infrared spectroscopy and N2 porosimetry. The evolution of COF crystallinity during the solvothermal depolymerization and repolymerization processes was characterized by in situ wide angle X-ray scattering, and the concentrations of free COF monomers as a function of temperature were quantified by variable temperature 1H NMR spectroscopy. The ability of a 2D COF to depolymerize under these conditions depends on both the identity of the COF and its initial materials quality. For one network formed at room temperature (TAPB-PDA COF), a first depolymerization process is nearly complete, and the repolymerization yields materials with dramatically enhanced crystallinity and surface area. Already recrystallized materials partially depolymerize upon heating their reaction mixtures a second time. A related 2D COF (TAPB-DMTA COF) forms initially with improved crystallinity compared to TAPB-PDA COF and then partially depolymerizes upon heating. These results suggest that both high materials quality and network-dependent properties, such as interlayer interaction strength, influence the extent to which 2D COFs resist depolymerization. These findings offer a new means to recrystallize or solvent anneal 2D COFs and may ultimately inform crystallization conditions for obtaining large-area imine-linked two-dimensional polymers from solution.

Dataset Information

Controlled growth of imine-linked two-dimensional covalent organic framework nanoparticles.

Publications

Controlled growth of imine-linked two-dimensional covalent organic framework nanoparticles.

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