Facile synthesis of heteroporous covalent organic frameworks with dual linkages: a “three-in-one” strategy

Abstract

Covalent organic frameworks (COFs) with dual linkages can combine advantages and properties of two distinct connectors, enabling the development of multifunctional materials. However, due to challenges in simultaneously forming two types of linkages, the synthesis of COFs with dual linkages remains a significant challenge. Herein, we propose a “three-in-one” molecular design strategy for synthesizing COFs with dual linkages (4-amino-4"-(2,2-dioxan-1,3-dioxan-5-yl)-[1,1':3',1"-terphenyl]-5'-yl) boronic acid (ADTB)-COF and (4'-amino-5'-(4-(2,2-dioxan-1,3-dioxan-5-yl)phenyl)-[1,1':3',1'-teroxan]-5-yl) boronic acid (ADPB)-COF through reversible condensation between three distinct functionalization groups on the monomer. Benefitting from the abundant micropores and high surface area, ADPB-COF showed excellent selective adsorption capability of C₃H₈ over CH₄ (174, 298 K/1 bar). The present work introduces a new approach for constructing COFs with dual linkages, which greatly simplifies the synthesis process and provides a novel opportunity to develop functional materials based on COFs with multi-linkages.

Keywords

Two-dimensional / covalent organic frameworks / dual linkages / light hydrocarbon / adsorption/separation

References

[1] Qian C,Qiao J.Linkage engineering by harnessing supramolecular interactions to fabricate 2D hydrazone-linked covalent organic framework platforms toward advanced catalysis.J Am Chem Soc2020;142:18138-49

[2] Song D,Li J.“All-in-one” covalent organic framework for photocatalytic CO₂ reduction.Chinese J Catal2022;43:2425-33

[3] Yang Z,Su X.Metallosalphen-based 2D covalent organic frameworks with an unprecedented tju topology via K-shaped two-in-one monomers.Chem Mater2022;34:5888-95

[4] Zhao Z,Li B.Spatial regulation of acceptor units in olefin-linked COFs toward highly efficient photocatalytic H₂ evolution.Adv Sci2022;9:2203832 PMCID:PMC9561862

[5] Díaz U.Ordered covalent organic frameworks, COFs and PAFs. From preparation to application.Coord Chem Rev2016;311:85-124

[6] Li J,Zou Y,Song Z.Achieving a stable COF with the combination of “flat” and “twist” large-size rigid synthons for selective gas adsorption and separation.Chin Chem Lett2022;33:3017-20

[7] Moroni M,Vismara R,Navarro JAR.Impact of pore flexibility in imine-linked covalent organic frameworks on benzene and cyclohexane adsorption.ACS Appl Mater Interfaces2022;14:40890-901 PMCID:PMC9931175

[8] Zhao Z,Kang C.Reversing adsorption and separation of 1-phenylethanol and acetophenone in organic phase via β-ketoenamine-linked covalent organic frameworks.Chem Eng J2023;454:140531

[9] Tong Y,Wang J,Zhang Q.Covalent organic framework containing dual redox centers as an efficient anode in Li-ion batteries.SmartMat2022;3:685-94

[10] Iqbal R,Hamza M.State of the art two-dimensional covalent organic frameworks: prospects from rational design and reactions to applications for advanced energy storage technologies.Coord Chem Rev2021;447:214152

[11] Patra BC.New covalent organic square lattice based on porphyrin and tetraphenyl ethylene building blocks toward high-performance supercapacitive energy storage.Chem Mater2021;33:8512-23

[12] Mohammed AK,Halder A.Weak intermolecular interactions in covalent organic framework-carbon nanofiber based crystalline yet flexible devices.ACS Appl Mater Interfaces2019;11:30828-37

[13] Wang C,Zhu Y,Wu J.2D covalent organic frameworks: from synthetic strategies to advanced optical-electrical-magnetic functionalities.Adv Mater2022;34:2102290

[14] Zhao R,Li J.Two-dimensional covalent organic frameworks for electrocatalysis: achievements, challenges, and opportunities.Nano Res2023;16:8570-95

[15] Zhang H,Huang J,Du K.Charge and mass transport mechanisms in two-dimensional covalent organic frameworks (2D COFs) for electrochemical energy storage devices.Energy Environ Sci2023;16:889-951

[16] Bhunia S,Gaharwar AK.2D covalent organic frameworks for biomedical applications.Adv Funct Mater2020;30:2002046

[17] Guo L,Li M,Song Y.Covalent organic frameworks for fluorescent sensing: recent developments and future challenges.Coord Chem Rev2021;440:213957

[18] Jiang S,Ma W.Dual-functional two-dimensional covalent organic frameworks for water sensing and harvesting.Mater Chem Front2021;5:4193-201

[19] Tan Z,Xu L.Simultaneous sensing of multiplex volatile organic compounds by adsorption and plasmon dual-induced raman enhancement technique.ACS Sens2023;8:867-74

[20] Liang RR,A RH.Two-dimensional covalent organic frameworks with hierarchical porosity.Chem Soc Rev2020;49:3920-51

[21] Zhi Y,Zhang HL.Recent progress in metal-free covalent organic frameworks as heterogeneous catalysts.Small2020;16:2001070

[22] Li C.Controllable synthesis and performance modulation of 2D covalent-organic frameworks.Small2021;17:2100918

[23] Zhang T,Chen L.2D conjugated covalent organic frameworks: defined synthesis and tailor-made functions.Acc Chem Res2022;55:795-808

[24] Xu J,Bu XH.Advances in emerging crystalline porous materials.Small2021;17:2102331

[25] Geng K,Xu H,Jiang D.Covalent organic frameworks: polymer chemistry and functional design.Prog Polym Sci2020;108:101288

[26] Côté AP,Ockwig NW,Matzger AJ.Porous, crystalline, covalent organic frameworks.Science2005;310:1166-70

[27] Romero-Muñiz I,Albacete P.Unveiling the local structure of palladium loaded into imine-linked layered covalent organic frameworks for cross-coupling catalysis.Angew Chem Int Ed Engl2020;59:13013-20

[28] Liang B,Wang J.Nonlinear optical properties of porphyrin-based covalent organic frameworks determined by steric-orientation of conjugation.J Mater Chem C2023;11:3354-9

[29] Helweh W,Wang S.Layered structures of assembled imine-linked macrocycles and two-dimensional covalent organic frameworks give rise to prolonged exciton lifetimes.J Mater Chem C2022;10:3015-26

[30] Das P.Flexible and semi-flexible amide-hydrazide decorated fluorescent covalent organic frameworks as on-off pH responsive proton scavengers.ACS Appl Mater Interfaces2021;13:14160-8

[31] Kang J,Chen B.Amide linkages in pyrene-based covalent organic frameworks toward efficient photocatalytic reduction of uranyl.ACS Appl Mater Interfaces2022;14:57225-34

[32] Zhou ZB,Qi QY,Ma DL.A facile, efficient, and general synthetic method to amide-linked covalent organic frameworks.J Am Chem Soc2022;144:1138-43

[33] Xiao Z,Tang Y.Covalent organic frameworks with lithiophilic and sulfiphilic dual linkages for cooperative affinity to polysulfides in lithium-sulfur batteries.Energy Stor Mater2018;12:252-9

[34] Castano I,Dos Reis R,Gianneschi NC.Mapping grains, boundaries, and defects in 2D covalent organic framework thin films.Chem Mater2021;33:1341-52 PMCID:PMC8922717

[35] Hu J,Ozdemir J.Applications of dynamic covalent chemistry concept towards tailored covalent organic framework nanomaterials: a review.ACS Appl Nano Mater2020;3:6239-69 PMCID:PMC8317485

[36] Jackson KT,El-Kaderi HM.Targeted synthesis of a porous borazine-linked covalent organic framework.Chem Commun2012;48:8823-5

[37] Hota MK,Lei Y.Electrochemical thin-film transistors using covalent organic framework channel.Adv Funct Mater2022;32:2201120

[38] Xu X,Xu K,Fan X.Janus Dione-based conjugated covalent organic frameworks with high conductivity as superior cathode materials.J Am Chem Soc2023;145:1022-30

[39] Zhao Y,Wu D.Ruthenium complex of sp² carbon-conjugated covalent organic frameworks as an efficient electrocatalyst for hydrogen evolution.Small2022;18:2107750

[40] Cheng YZ,Wu X,Liu XF.Persistent radical cation sp² carbon-covalent organic framework for photocatalytic oxidative organic transformations.Appl Catal B Environ2022;306:121110

[41] Yue JY,Wang YT.Dual functional sp² carbon-conjugated covalent organic frameworks for fluorescence sensing and effective removal and recovery of Pd²⁺ ions.J Mater Chem A2021;9:26861-6

[42] Liang RR,Xu SQ,Zhao X.Fabricating organic nanotubes through selective disassembly of two-dimensional covalent organic frameworks.J Am Chem Soc2020;142:70-4

[43] Zeng Y,Luo Z.Covalent organic frameworks formed with two types of covalent bonds based on orthogonal reactions.J Am Chem Soc2015;137:1020-3

[44] Hu J,Lin Z,Liao S.Construction of a hollow spherical covalent organic framework with olefin and imine dual linkages based on orthogonal reactions.Chem Mater2022;34:5249-57

[45] Xu X,Xu K,Chen H.Pore partition in two-dimensional covalent organic frameworks.Nat Commun2023;14:3360 PMCID:PMC10250421

[46] Smith BJ.Mechanistic studies of two-dimensional covalent organic frameworks rapidly polymerized from initially homogenous conditions.J Am Chem Soc2014;136:8783-9

[47] Li Y,Xu T.De novo design and facile synthesis of 2D covalent organic frameworks: a two-in-one strategy.J Am Chem Soc2019;141:13822-8

[48] Li Y,Xing G,Chen L.New synthetic strategies toward covalent organic frameworks.Chem Soc Rev2020;49:2852-68

[49] Li Y,Zheng W.Targeted synthesis of isomeric naphthalene-based 2D kagome covalent organic frameworks.Angew Chem Int Ed Engl2023;62:e202216795

[50] Li G.Micro- and ultramicroporous polyaminals for highly efficient adsorption/separation of C₁-C₃ hydrocarbons and CO₂ in natural gas.ACS Appl Mater Interfaces2020;12:24488-97

[51] Zhang S,Jiang L,Zhu G.Light hydrocarbon separations using porous organic framework materials.Chemistry2020;26:3205-21

[52] Li JR,Zhou HC.Selective gas adsorption and separation in metal-organic frameworks.Chem Soc Rev2009;38:1477-504