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Designed synthesis of double-stage two-dimensional covalent organic frameworks.

ABSTRACT: Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers in which organic building blocks are covalently and topologically linked to form extended crystalline polygon structures, constituting a new platform for designing π-electronic porous materials. However, COFs are currently synthesised by a few chemical reactions, limiting the access to and exploration of new structures and properties. The development of new reaction systems that avoid such limitations to expand structural diversity is highly desired. Here we report that COFs can be synthesised via a double-stage connection that polymerises various different building blocks into crystalline polygon architectures, leading to the development of a new type of COFs with enhanced structural complexity and diversity. We show that the double-stage approach not only controls the sequence of building blocks but also allows fine engineering of pore size and shape. This strategy is widely applicable to different polymerisation systems to yield hexagonal, tetragonal and rhombus COFs with predesigned pores and π-arrays.

SUBMITTER: Chen X

PROVIDER: S-EPMC4600973 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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Designed synthesis of double-stage two-dimensional covalent organic frameworks.

Chen Xiong X Addicoat Matthew M Jin Enquan E Xu Hong H Hayashi Taku T Xu Fei F Huang Ning N Irle Stephan S Jiang Donglin D

Scientific reports 20151012

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers in which organic building blocks are covalently and topologically linked to form extended crystalline polygon structures, constituting a new platform for designing π-electronic porous materials. However, COFs are currently synthesised by a few chemical reactions, limiting the access to and exploration of new structures and properties. The development of new reaction systems that avoid such limitations to expa ...[more]

PMID: 26456081

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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

Designed synthesis of double-stage two-dimensional covalent organic frameworks.

Publications

Designed synthesis of double-stage two-dimensional covalent organic frameworks.

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