Title: Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks

Abstract

Abstract The growing interest in two-dimensional imine-based covalent organic frameworks (COFs) is inspired by their crystalline porous structures and the potential for extensive π-electron delocalization. The intrinsic reversibility and strong polarization of imine linkages, however, leads to insufficient chemical stability and optoelectronic properties. Developing COFs with improved robustness and π-delocalization is highly desirable but remains an unsettled challenge. Here we report a facile strategy that transforms imine-linked COFs into ultrastable porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction. The as-formed, quinoline-linked COFs not only retain crystallinity and porosity, but also display dramatically enhanced chemical stability over their imine-based COF precursors, rendering them among the most robust COFs up-to-date that can withstand strong acidic, basic and redox environment. Owing to the chemical diversity of the cycloaddition reaction and structural tunability of COFs, the pores of COFs can be readily engineered to realize pre-designed surface functionality.

Authors:

Li, Xinle; Zhang, Changlin ;

• Search DOE PAGES for author "Zhang, Changlin"
• Search DOE PAGES for ORCID "0000-0002-1207-4264"

Cai, Songliang; Lei, Xiaohe; Altoe, Virginia; Hong, Fang; Urban, Jeffrey J.; Ciston, Jim; Chan, Emory M.; Liu, Yi

• Search DOE PAGES for author "Liu, Yi"
• Search DOE PAGES for ORCID "0000-0002-3954-6102"

Publication Date:

Tue Jul 31 00:00:00 EDT 2018

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)

OSTI Identifier:

1461610

Alternate Identifier(s):

OSTI ID: 1477418

Grant/Contract Number:  

AC02-05CH11231; 21603076

Resource Type:

Published Article

Journal Name:

Nature Communications

Additional Journal Information:

Journal Name: Nature Communications Journal Volume: 9 Journal Issue: 1; Journal ID: ISSN 2041-1723

Publisher:

Nature Publishing Group

Country of Publication:

United Kingdom

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polymer synthesis; polymers; porous materials