Online citations, reference lists, and bibliographies.
← Back to Search

Moving Beyond Boron: The Emergence Of New Linkage Chemistries In Covalent Organic Frameworks

Catherine R. DeBlase, William R Dichtel
Published 2016 · Chemistry

Save to my Library
Download PDF
Analyze on Scholarcy
Share
Since their discovery in 2005, covalent organic frameworks (COFs) have attracted interest as potential materials for gas storage, catalysis, energy storage, and other applications because of their ability to periodically and reliably organize designed functionality into high surface area materials. Most of the first examples relied on boron-containing linkages, which suffer from hydrolytic and oxidative instability that limit their utility. In this Perspective, we describe the trend toward more robust linkages by highlighting the design, synthesis, and properties of several recent examples. The continued development of new COF chemistries, along with improved understanding of their formation and control of their final form, will provide a means to harness their molecularly precise solid-state structures for useful purposes.
This paper references
10.1039/C39740000254
Tetracyanomuconitritebis(tetrathiafulvalene): the first complex salt of tetrathiafulvalene
F. Wudl (1974)
10.1021/ACS.CHEMMATER.5B04388
Sequential Pore Wall Modification in a Covalent Organic Framework for Application in Lactic Acid Adsorption
Maria S. Lohse (2016)
10.1021/acsnano.5b00184
Rapid and efficient redox processes within 2D covalent organic framework thin films.
Catherine R. DeBlase (2015)
10.1039/c5cc04679c
Few-layer, large-area, 2D covalent organic framework semiconductor thin films.
J. Feldblyum (2015)
10.1039/C4RA09304F
Bottom-up approach to engineer a molybdenum-doped covalent-organic framework catalyst for selective oxidation reaction
Weijie Zhang (2014)
10.1021/ja206242v
A 2D covalent organic framework with 4.7-nm pores and insight into its interlayer stacking.
Eric L. Spitler (2011)
10.1021/ja308278w
Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route.
S. Kandambeth (2012)
10.1038/ncomms3736
Conjugated organic framework with three-dimensionally ordered stable structure and delocalized π clouds
Jia Guo (2013)
10.1021/jacs.5b09487
Desymmetrized Vertex Design for the Synthesis of Covalent Organic Frameworks with Periodically Heterogeneous Pore Structures.
Youlong Zhu (2015)
10.1039/C4TA00523F
Covalent-organic frameworks: potential host materials for sulfur impregnation in lithium–sulfur batteries
Huaping Liao (2014)
10.1039/c3cc49176e
Highly stable covalent organic framework-Au nanoparticles hybrids for enhanced activity for nitrophenol reduction.
Pradip Pachfule (2014)
10.1002/anie.201107070
Lattice expansion of highly oriented 2D phthalocyanine covalent organic framework films.
Eric L. Spitler (2012)
10.1021/ja4017842
Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks.
B. P. Biswal (2013)
10.1038/ncomms8786
Rational design of crystalline supermicroporous covalent organic frameworks with triangular topologies
Sasanka Dalapati (2015)
10.1016/J.POLYMER.2013.07.030
Functionalization of 3D covalent organic frameworks using monofunctional boronic acids
Spencer D. Brucks (2014)
10.1002/chem.201403800
A covalent organic framework-cadmium sulfide hybrid as a prototype photocatalyst for visible-light-driven hydrogen production.
J. Thote (2014)
10.1021/jacs.5b04300
Tailor-Made Pore Surface Engineering in Covalent Organic Frameworks: Systematic Functionalization for Performance Screening.
N. Huang (2015)
10.1039/c3cs60358j
Organic cage compounds--from shape-persistency to function.
G. Zhang (2014)
10.1002/adma.200903436
Rational extension of the family of layered, covalent, triazine-based frameworks with regular porosity.
Michael J Bojdys (2010)
10.1039/c5cc10221a
Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks.
B. Smith (2016)
10.1021/ja509602c
Locking covalent organic frameworks with hydrogen bonds: general and remarkable effects on crystalline structure, physical properties, and photochemical activity.
Xiong Chen (2015)
10.1016/0038-1098(74)90915-6
Apparent giant conductivity peaks in an anisotropic medium: TTF-TCNQ
D. Schafer (1974)
10.1002/anie.201108462
Internal functionalization of three-dimensional covalent organic frameworks.
D. Bunck (2012)
10.1039/C4SC02593H
Tunable electrical conductivity in oriented thin films of tetrathiafulvalene-based covalent organic framework
Songliang Cai (2014)
10.1126/science.1120411
Porous, Crystalline, Covalent Organic Frameworks
A. P. Côté (2005)
10.1039/c3cc40358k
Postsynthetic functionalization of 3D covalent organic frameworks.
D. Bunck (2013)
10.1021/ja5037868
Mechanistic studies of two-dimensional covalent organic frameworks rapidly polymerized from initially homogenous conditions.
B. Smith (2014)
10.1126/science.1230444
The Chemistry and Applications of Metal-Organic Frameworks
H. Furukawa (2013)
10.1021/jacs.5b04147
3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery.
Q. Fang (2015)
10.1002/anie.201411262
Two-Dimensional Covalent Organic Frameworks for Carbon Dioxide Capture through Channel-Wall Functionalization
N. Huang (2015)
10.1002/adma.201200751
Porous, fluorescent, covalent triazine-based frameworks via room-temperature and microwave-assisted synthesis.
Shijie Ren (2012)
10.1039/C4SC00016A
A hydrazone-based covalent organic framework for photocatalytic hydrogen production
Linus Stegbauer (2014)
10.1021/ja8096256
A crystalline imine-linked 3-D porous covalent organic framework.
Fernando J Uribe-Romo (2009)
10.1002/anie.200801863
Two-dimensional polymers: just a dream of synthetic chemists?
Junji Sakamoto (2009)
10.1002/chem.201402844
Two-dimensional tetrathiafulvalene covalent organic frameworks: towards latticed conductive organic salts.
Shangbin Jin (2014)
10.1002/adma.200800030
Tailoring microporosity in covalent organic frameworks.
R. Tilford (2008)
10.1039/c3cc48813f
Catalytic covalent organic frameworks via pore surface engineering.
H. Xu (2014)
10.1021/ja409421d
β-Ketoenamine-linked covalent organic frameworks capable of pseudocapacitive energy storage.
Catherine R. DeBlase (2013)
10.1002/anie.201501706
Radical covalent organic frameworks: a general strategy to immobilize open-accessible polyradicals for high-performance capacitive energy storage.
F. Xu (2015)
10.1002/anie.201509014
Ionic Covalent Organic Frameworks with Spiroborate Linkage.
Y. Du (2016)
10.1039/C4TA00284A
Multifunctional and robust covalent organic framework–nanoparticle hybrids
Pradip Pachfule (2014)
10.1038/nchem.695
Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks.
Eric L. Spitler (2010)
10.1021/ja408243n
Bulk synthesis of exfoliated two-dimensional polymers using hydrazone-linked covalent organic frameworks.
D. Bunck (2013)
10.1002/anie.201310500
3D microporous base-functionalized covalent organic frameworks for size-selective catalysis.
Q. Fang (2014)
10.1002/anie.201300256
A squaraine-linked mesoporous covalent organic framework.
A. Nagai (2013)
10.1021/ja408121p
Chemically stable multilayered covalent organic nanosheets from covalent organic frameworks via mechanical delamination.
S. Chandra (2013)
10.1038/ncomms5503
Designed synthesis of large-pore crystalline polyimide covalent organic frameworks.
Q. Fang (2014)
10.1126/science.aac8343
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
S. Lin (2015)
10.1002/chem.201405330
A tetrathiafulvalene-based electroactive covalent organic framework.
H. Ding (2014)
10.1039/c4cc01825g
Towards covalent organic frameworks with predesignable and aligned open docking sites.
Xiong Chen (2014)
10.1039/B600349D
Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage.
N. McKeown (2006)
10.1039/c2cs35157a
Covalent organic frameworks.
Xiao Feng (2012)
10.1002/anie.200803826
A belt-shaped, blue luminescent, and semiconducting covalent organic framework.
S. Wan (2008)
10.1021/ja508693y
Structural evolution of 2D microporous covalent triazine-based framework toward the study of high-performance supercapacitors.
Long Hao (2015)
10.1038/nmat2545
Porous organic cages.
Tomokazu Tozawa (2009)
10.1038/nmat4611
Proton conduction in crystalline and porous covalent organic frameworks.
H. Xu (2016)
10.1002/anie.201306775
Enhancement of chemical stability and crystallinity in porphyrin-containing covalent organic frameworks by intramolecular hydrogen bonds.
S. Kandambeth (2013)
10.1021/ar1000617
Rational design, synthesis, purification, and activation of metal-organic framework materials.
O. Farha (2010)
10.1038/nchem.1628
Rationally synthesized two-dimensional polymers.
John W Colson (2013)
10.1039/c5cc02147b
A triazine-based covalent organic polymer for efficient CO2 adsorption.
R. Gomes (2015)
10.1021/CM303751N
Covalent Triazine Frameworks Prepared from 1,3,5-Tricyanobenzene
P. Katekomol (2013)
10.1021/ja204728y
Crystalline covalent organic frameworks with hydrazone linkages.
Fernando J Uribe-Romo (2011)
10.1038/ncomms1542
Pore surface engineering in covalent organic frameworks.
A. Nagai (2011)
10.1039/c5sc00894h
Mesoporous 2D covalent organic frameworks based on shape-persistent arylene-ethynylene macrocycles† †Electronic supplementary information (ESI) available: Experimental procedures, TGA, FT-IR, PXRD and NMR spectra of compounds. See DOI: 10.1039/c5sc00894h
Haishen Yang (2015)
10.1021/ja502212v
Phosphoric acid loaded azo (-N═N-) based covalent organic framework for proton conduction.
S. Chandra (2014)
10.1038/nchem.2352
Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts.
H. Xu (2015)
10.1039/c4cc05665e
A 2D azine-linked covalent organic framework for gas storage applications.
Zhong-ping Li (2014)
10.1021/ja206846p
Construction of covalent organic framework for catalysis: Pd/COF-LZU1 in Suzuki-Miyaura coupling reaction.
San-Yuan Ding (2011)
10.1021/ja4103293
An azine-linked covalent organic framework.
Sasanka Dalapati (2013)
10.1021/CM201140R
Covalent Organic Frameworks with High Charge Carrier Mobility
Shun Wan (2011)
10.1039/c2cs35072f
Covalent organic frameworks (COFs): from design to applications.
San-Yuan Ding (2013)
10.1039/C4CY00969J
Bottom-up approach to engineer two covalent porphyrinic frameworks as effective catalysts for selective oxidation
W. Zhang (2015)
10.1002/anie.200705710
Porous, covalent triazine-based frameworks prepared by ionothermal synthesis.
P. Kuhn (2008)
10.1002/chem.201201351
Permanent porous materials from discrete organic molecules-towards ultra-high surface areas.
M. Mastalerz (2012)
10.1039/c4cc03389b
Mechanosynthesis of imine, β-ketoenamine, and hydrogen-bonded imine-linked covalent organic frameworks using liquid-assisted grinding.
G. Das (2014)
10.1039/C4TA00555D
Green, scalable and morphology controlled synthesis of nanofibrous covalent organic frameworks and their nanohybrids through a vapor-assisted solid-state approach
Y. Jiang (2014)
10.1039/C3EE42548G
A perfluorinated covalent triazine-based framework for highly selective and water–tolerant CO2 capture
Y. Zhao (2013)



This paper is referenced by
10.1039/c8cs00657a
Emerging porous materials in confined spaces: from chromatographic applications to flow chemistry.
J. Zhang (2019)
10.1002/anie.201914233
A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor-Acceptor Fulleretic Covalent-Organic Materials.
N. Shustova (2020)
10.1002/ANGE.201713359
Heißes Wasser ermöglicht Kristallinität in organischen Materialien
Miriam M Unterlass (2018)
10.1021/acscentsci.7b00127
Covalent Organic Frameworks as a Platform for Multidimensional Polymerization
Ryan P Bisbey (2017)
10.1021/jacs.7b06913
Synthesis of 2D Imine-Linked Covalent Organic Frameworks through Formal Transimination Reactions.
Edon Vitaku (2017)
10.1016/J.PROGPOLYMSCI.2018.09.006
Architecture-transformable polymers: Reshaping the future of stimuli-responsive polymers
H. Sun (2019)
10.1002/CNMA.201700048
Two‐Dimensional Covalent Organic Frameworks for Optoelectronics and Energy Storage
A. Mandal (2017)
10.1039/d0mh01710h
Porous flexible frameworks: origins of flexibility and applications
Saona Seth (2021)
10.1002/anie.201806202
Stack the Bowls: Tailoring the Electronic Structure of Corannulene-Integrated Crystalline Materials.
A. Rice (2018)
10.1002/chem.201800459
Equilibration of Imine-Linked Polymers to Hexagonal Macrocycles Driven by Self-Assembly.
A. Chavez (2018)
10.1021/jacs.7b05555
Computational and Experimental Studies on the Effects of Monomer Planarity on Covalent Organic Framework Formation.
Christina M. Thompson (2017)
10.1039/c8cc08957d
Improved synthesis of β-ketoenamine-linked covalent organic frameworks via monomer exchange reactions.
M. C. Daugherty (2019)
10.1002/solr.202000339
Bioinspired NADH Regeneration Based on Conjugated Photocatalytic Systems
Y. Zhang (2020)
10.1016/j.micromeso.2019.109700
Integration of α-amylase into covalent organic framework for highly efficient biocatalyst
A. Samui (2020)
10.1016/J.CHEMPR.2017.12.011
Lewis-Acid-Catalyzed Interfacial Polymerization of Covalent Organic Framework Films
M. Matsumoto (2018)
10.1016/J.POLYMER.2016.12.052
1,4-Phenylenediamine based covalent triazine framework as an electro catalyst
S. Gopi (2017)
10.1021/jacs.7b06640
Selective Molecular Separation by Interfacially Crystallized Covalent Organic Framework Thin Films.
K. Dey (2017)
10.1039/c9cc05674b
Covalent organic frameworks from a monomer with reduced symmetry: polymorphism and Sierpiński triangles.
D. Cui (2019)
10.1039/c8cs00978c
Post-synthetic modification of covalent organic frameworks.
J. Segura (2019)
10.1021/jacs.7b09169
Nucleation and Growth of Covalent Organic Frameworks from Solution: The Example of COF-5.
H. Li (2017)
10.1039/c9cs00807a
The luminescent and photophysical properties of covalent organic frameworks.
W. Haug (2020)
10.1021/jacs.6b12328
Stable Covalent Organic Frameworks for Exceptional Mercury Removal from Aqueous Solutions.
N. Huang (2017)
10.1021/jacs.7b01240
Rapid, Low Temperature Formation of Imine-Linked Covalent Organic Frameworks Catalyzed by Metal Triflates.
Michio Matsumoto (2017)
10.1002/anie.201906976
2D Poly(arylene vinylene) Covalent Organic Frameworks via Aldol Condensation of Trimethyltriazine.
T. Jadhav (2019)
10.1016/J.CHEMPR.2018.05.003
Covalent Organic Frameworks Linked by Amine Bonding for Concerted Electrochemical Reduction of CO2
Haoyu Liu (2018)
10.1002/cssc.201700801
Two-Dimensional Materials as Prospective Scaffolds for Mixed-Matrix Membrane-Based CO2 Separation.
X. Zhu (2017)
10.1039/c8cc05225e
Dramatic improvement of stability by in situ linker cyclization of a metal-organic framework.
Y. Hou (2018)
10.1038/s41578-020-00254-z
Polymer photocatalysts for solar-to-chemical energy conversion
T. Banerjee (2020)
10.1039/C8TA09070J
Two-dimensional nanosheet-based gas separation membranes
M. Liu (2018)
10.1039/d0qo00083c
Discrete boronate ester ladders from the dynamic covalent self-assembly of oligo(phenylene ethynylene) derivatives and phenylenebis(boronic acid)
Vasileios Drogkaris (2020)
10.1021/jacs.9b07383
A Wavy Two-Dimensional Covalent Organic Framework from Core-Twisted Polycyclic Aromatic Hydrocarbons.
Marta Martínez-Abadía (2019)
10.1007/s00894-018-3676-x
A 2D covalent organic framework as a sensor for detecting formaldehyde
Y. Wang (2018)
See more
Semantic Scholar Logo Some data provided by SemanticScholar