Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification

被引：129

作者：

Grunenberg, Lars ^{[1
,2
]}

Savasci, Goekcen ^{[1
,2
,3
,4
]}

Terban, Maxwell W. ^{[1
]}

Duppel, Viola ^{[1
]}

Moudrakovski, Igor ^{[1
]}

Etter, Martin ^{[5
]}

Dinnebier, Robert E. ^{[1
]}

Ochsenfeld, Christian ^{[1
,2
,3
,4
]}

Lotsch, Bettina V. ^{[1
,2
,3
,4
]}

机构：

[1] Max Planck Inst Solid State Res, D-70569 Stuttgart, Germany

[2] Ludwig Maximilians Univ Munchen, Dept Chem, D-81377 Munich, Germany

[3] E Convers, Lichtenbergstr 4a, D-85748 Garching, Germany

[4] Ctr NanoSci, D-80799 Munich, Germany

[5] Deutsch Elektronen Synchrotron DESY, D-22607 Hamburg, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2021年 / 143卷 / 09期

关键词：

REDUCTION; LINKAGES;

D O I：

10.1021/jacs.0c12249

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Covalent organic frameworks have emerged as a powerful synthetic platform for installing and interconverting dedicated molecular functions on a crystalline polymeric backbone with atomic precision. Here, we present a novel strategy to directly access amine-linked covalent organic frameworks, which serve as a scaffold enabling pore-wall modification and linkage-interconversion by new synthetic methods based on Leuckart-Wallach reduction with formic acid and ammonium formate. Frameworks connected entirely by secondary amine linkages, mixed amine/imine bonds, and partially formylated amine linkages are obtained in a single step from imine-linked frameworks or directly from corresponding linkers in a one-pot crystallization- reduction approach. The new, 2D amine-linked covalent organic frameworks, rPI-3-COF, rTTI-COF, and rPy1P-COF, are obtained with high crystallinity and large surface areas. Secondary amines, installed as reactive sites on the pore wall, enable further postsynthetic functionalization to access tailored covalent organic frameworks, with increased hydrolytic stability, as potential heterogeneous catalysts.

引用

页码：3430 / 3438

页数：9