TY - JOUR
T1 - Rapid, Low Temperature Formation of Imine-Linked Covalent Organic Frameworks Catalyzed by Metal Triflates
AU - Matsumoto, Michio
AU - Dasari, Raghunath R.
AU - Ji, Woojung
AU - Feriante, Cameron H.
AU - Parker, Timothy C.
AU - Marder, Seth R.
AU - Dichtel, William R.
N1 - Funding Information:
W.R.D. and S.R.M. acknowledge the United States Army Research Office for a Multidisciplinary University Research Initiative (MURI) award under grant number W911NF-15-1-0447. W.R.D. was also supported by the Camille and Henry Dreyfus Foundation through a Camille Dreyfus Teacher-Scholar Award. We also made use of the Cornell Center for Materials Research Shared Facilities, which are supported through the NSF MRSEC program (DMR-1120296). We thank Christian S. Diercks for helpful discussions.
Publisher Copyright:
© 2017 American Chemical Society.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2017/4/12
Y1 - 2017/4/12
N2 - Imine-linked two-dimensional covalent organic frameworks (2D COFs) are crystalline polymer networks with enhanced stability compared to boronate ester-linked systems and with broad monomer scope. They are traditionally prepared by condensing polyfunctional aldehydes and amines at elevated temperature in a mixture of organic solvents and aqueous CH 3 CO 2 H, which catalyzes imine formation and exchange. Here we employ metal triflates, which are water-tolerant Lewis acids, to accelerate 2D imine-linked COF synthesis and improve their materials quality. Low catalyst loadings provide crystalline polymer networks in nearly quantitative yields. These conditions are demonstrated for several COFs, including heteroatom-containing systems of interest for optoelectronic applications.
AB - Imine-linked two-dimensional covalent organic frameworks (2D COFs) are crystalline polymer networks with enhanced stability compared to boronate ester-linked systems and with broad monomer scope. They are traditionally prepared by condensing polyfunctional aldehydes and amines at elevated temperature in a mixture of organic solvents and aqueous CH 3 CO 2 H, which catalyzes imine formation and exchange. Here we employ metal triflates, which are water-tolerant Lewis acids, to accelerate 2D imine-linked COF synthesis and improve their materials quality. Low catalyst loadings provide crystalline polymer networks in nearly quantitative yields. These conditions are demonstrated for several COFs, including heteroatom-containing systems of interest for optoelectronic applications.
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U2 - 10.1021/jacs.7b01240
DO - 10.1021/jacs.7b01240
M3 - Article
C2 - 28345908
AN - SCOPUS:85018312859
SN - 0002-7863
VL - 139
SP - 4999
EP - 5002
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 14
ER -