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Title: Entanglement of Square Nets in Covalent Organic Frameworks

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1]; ORCiD logo [2];  [3];  [1];  [4]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States). Berkeley Global Science Institute; Kavli Energy NanoScience Institute, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States). Berkeley Global Science Institute; Kavli Energy NanoScience Institute, Berkeley, CA (United States); United Arab Emirates Univ., Al Ain (United Arab Emirates)
  3. ShanghaiTech Univ. (China)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

Herein, two entangled 2D square covalent organic frameworks (COFs) have been synthesized from 4,4',4'',4'''-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)-tetrabenzaldehhyde (SFTB) and p-phenylenediamine (PPA) and benzidine (BZD) to form COF-38, [(SFTB)(PPA)2]imine, and its isoreticular form COF-39, [(SFTB)(BZD)2]imine. We also report the single-crystal electron diffraction structure of COF-39 and find that it is composed of mutually entangled 2D square nets (sql). These COFs represent the first examples of entangled 2D COF structures, which, as we illustrate, were made possible by our strategy of using the distorted tetrahedral SFTB building unit. SFTB overcomes the propensity of 2D COFs to stack through π-π stacking and allows entanglements to form. This work significantly adds to the design principles of COFs.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Natural Science Foundation of China; ShanghaiTech University
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1968253
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 144; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (29)

Design of higher valency in covalent organic frameworks journal October 2020
Covalent organic frameworks journal January 2012
Covalent Organic Frameworks: Structures, Synthesis, and Applications journal July 2018
A Pyrene-Based, Fluorescent Three-Dimensional Covalent Organic Framework journal March 2016
Tuning the Topology of Three-Dimensional Covalent Organic Frameworks via Steric Control: From pts to Unprecedented ljh journal May 2021
Porous, Crystalline, Covalent Organic Frameworks journal November 2005
High-symmetry embeddings of interpenetrating periodic nets. Essential rings and patterns of catenation journal January 2015
Reticular design and crystal structure determination of covalent organic frameworks journal January 2021
3D Cage COFs: A Dynamic Three-Dimensional Covalent Organic Framework with High-Connectivity Organic Cage Nodes journal September 2020
Observation of Interpenetration Isomerism in Covalent Organic Frameworks journal April 2018
Approaches and challenges in the synthesis of three-dimensional covalent-organic frameworks journal December 2018
Designed Synthesis of 3D Covalent Organic Frameworks journal April 2007
Scanning reciprocal space for solving unknown structures: energy filtered diffraction tomography and rotation diffraction tomography methods journal January 2013
How 2-periodic coordination networks are interweaved: entanglement isomerism and polymorphism journal January 2017
Covalent Organic Frameworks: Design, Synthesis, and Functions journal January 2020
A Crystalline Imine-Linked 3-D Porous Covalent Organic Framework
  • Uribe-Romo, Fernando J.; Hunt, Joseph R.; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 131, Issue 13, p. 4570-4571 https://doi.org/10.1021/ja8096256
journal April 2009
Introduction to Reticular Chemistry journal January 2019
Three-Dimensional Large-Pore Covalent Organic Framework with stp Topology journal July 2020
Chemistry of Covalent Organic Frameworks journal November 2015
Three-Dimensional Covalent Organic Framework with ceq Topology journal December 2020
Tuning the stacking behaviour of a 2D covalent organic framework through non-covalent interactions journal January 2017
Single-crystal x-ray diffraction structures of covalent organic frameworks journal July 2018
Interpenetrating Nets: Ordered, Periodic Entanglement journal June 1998
Solving the COF trilemma: towards crystalline, stable and functional covalent organic frameworks journal January 2020
Covalent Organic Frameworks: Chemistry beyond the Structure journal November 2018
Weaving of organic threads into a crystalline covalent organic framework journal January 2016
Design and applications of three dimensional covalent organic frameworks journal January 2020
The atom, the molecule, and the covalent organic framework journal March 2017
Self-templated synthesis of uniform hollow spheres based on highly conjugated three-dimensional covalent organic frameworks journal November 2020