Modulating Carrier Transfer over Carbazolic Conjugated Microporous Polymers via Donor Structural Design for Functionalization of Thiophenols.

Developing photocatalysts to steer conversion of solar energy toward high-value-added fine chemicals represents a potentially viable approach to address the energy crisis and environmental issues. However, enablement of this conversion is usually impeded by the sluggish kinetic process for proton-coupled electron transfer and rapid recombination of photogenerated excitons. Herein, we report a simple and general structural expansion strategy to facilitate charge transfer in conjugated microporous polymers (CMPs) via engineering the donor surrounding the trifluoromethylphenyl core. The resulting CMPs combine high surface area, strong light-harvesting capabilities, and tunable optical properties endowed by extended π-conjugation; the optimized compound CbzCMP-5 generated from 9,9',9″-(2-(trifluoromethyl)benzene-1,3,5-triyl)tris(9H-carbazole) remarkably enhanced the photogenerated carrier transfer efficiency, enabling the functionalization of thiophenols toward thiocarbamates and 3-sulfenylindoles with high photocatalytic efficiency. Most importantly, the in-depth insights into the carrier-transfer processes open up new prospects on further optimization and rational design of photoactive polymers for efficient charge-transfer-mediated reactions.

[1]  Han-jie Zhang,et al.  Highly-crystalline Triazine-PDI Polymer with an Enhanced Built-in Electric Field for Full-Spectrum Photocatalytic Phenol Mineralization , 2021, Applied Catalysis B: Environmental.

[2]  Shijie Ren,et al.  Boosting the Photocatalytic Hydrogen Evolution Activity for D–π–A Conjugated Microporous Polymers by Statistical Copolymerization , 2021, Advanced materials.

[3]  Xianjun Lang,et al.  Designing fluorene-based conjugated microporous polymers for blue light-driven photocatalytic selective oxidation of amines with oxygen , 2021 .

[4]  Hai‐Long Jiang,et al.  Microenvironment Modulation in Metal–Organic Framework-Based Catalysis , 2021, Accounts of Materials Research.

[5]  O. Reiser,et al.  Visible‐Light‐Induced Homolysis of Earth‐Abundant Metal‐Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis , 2021, Angewandte Chemie.

[6]  P. Cheng,et al.  Fabrication of Robust Covalent Organic Frameworks for Enhanced Visible-Light-Driven H2 Evolution , 2021 .

[7]  Daize Mo,et al.  Modulating Benzothiadiazole-Based Covalent Organic Frameworks via Halogenation for Enhanced Photocatalytic Water Splitting: Small Changes Make Big Differences. , 2020, Angewandte Chemie.

[8]  Bo Wang,et al.  Fully Conjugated Donor–Acceptor Covalent Organic Frameworks for Photocatalytic Oxidative Amine Coupling and Thioamide Cyclization , 2020 .

[9]  M. Caussanel,et al.  Open-Circuit Voltage Decay Simulations on Silicon and Gallium Arsenide p-n Homojunctions: Design Influences on Bulk Lifetime Extraction , 2020, Microelectron. J..

[10]  H. Tian,et al.  Fluorinated conjugated poly(benzotriazole)/g-C3N4 heterojunctions for significantly enhancing photocatalytic H2 evolution , 2020 .

[11]  Qingquan Liu,et al.  Ferrocenyl building block constructing porous organic polymer for gas capture and methyl violet adsorption , 2020, Journal of Central South University.

[12]  Qiang Zhao,et al.  Donor–Acceptor Charge Migration System of Superhydrophilic Covalent Triazine Framework and Carbon Nanotube toward High Performance Solar Thermal Conversion , 2020 .

[13]  Dongyun Chen,et al.  Surface Engineering of g‐C 3 N 4 by Stacked BiOBr Sheets Rich in Oxygen Vacancies for Boosting Photocatalytic Performance , 2020, Angewandte Chemie.

[14]  M. Oshikiri,et al.  Intermolecular cascaded π-conjugation channels for electron delivery powering CO2 photoreduction , 2020, Nature Communications.

[15]  Wei Chen,et al.  Programming Covalent Organic Frameworks for Photocatalysis: Investigation of Chemical and Structural Variations , 2020 .

[16]  Donghai Mei,et al.  Single-Atom Pt–N3 Sites on the Stable Covalent Triazine Framework Nanosheets for Photocatalytic N2 Fixation , 2020 .

[17]  Xiaojun Wu,et al.  Acetylene and Diacetylene Functionalized Covalent Triazine Frameworks as Metal‐Free Photocatalysts for Hydrogen Peroxide Production: A New Two‐Electron Water Oxidation Pathway , 2019, Advanced materials.

[18]  Hong Xia,et al.  Conjugated Microporous Polymers as Heterogeneous Photocatalysts for Efficient Degradation of a Mustard-Gas Simulant. , 2019, ACS applied materials & interfaces.

[19]  Y. Niu,et al.  Design of D–A1–A2 Covalent Triazine Frameworks via Copolymerization for Photocatalytic Hydrogen Evolution , 2019, ACS Catalysis.

[20]  Souvik Roy,et al.  Visible‐Light‐Driven CO2 Reduction by Mesoporous Carbon Nitride Modified with Polymeric Cobalt Phthalocyanine , 2019, Angewandte Chemie.

[21]  Zhengxiao Guo,et al.  Tunable Covalent Triazine-Based Frameworks (CTF-0) for Visible-Light-Driven Hydrogen and Oxygen Generation from Water Splitting , 2019, ACS catalysis.

[22]  Xinchen Wang,et al.  2D sp2 Carbon-Conjugated Covalent Organic Frameworks for Photocatalytic Hydrogen Production from Water , 2019, Chem.

[23]  Hong Xia,et al.  Construction of donor-acceptor type conjugated microporous polymers: A fascinating strategy for the development of efficient heterogeneous photocatalysts in organic synthesis , 2019, Applied Catalysis B: Environmental.

[24]  W. Ou,et al.  Photocatalytic Cascade Radical Cyclization Approach to Bioactive Indoline-Alkaloids over Donor–Acceptor Type Conjugated Microporous Polymer , 2019, ACS Catalysis.

[25]  Zi-long Tang,et al.  Iodine-Catalyzed Odorless Synthesis of S-Thiocarbamates with Sulfonyl Chlorides as a Sulfur Source. , 2019, The Journal of organic chemistry.

[26]  Liping Guo,et al.  Layered Thiazolo[5,4- d] Thiazole-Linked Conjugated Microporous Polymers with Heteroatom Adoption for Efficient Photocatalysis Application. , 2019, ACS applied materials & interfaces.

[27]  Pengpeng Shao,et al.  Ferrocene-Linkage-Facilitated Charge Separation in Conjugated Microporous Polymers. , 2019, Angewandte Chemie.

[28]  Pengpeng Shao,et al.  Ferrocene-Linkage-Facilitated Charge Separation in Conjugated Microporous Polymers. , 2019, Angewandte Chemie.

[29]  Bao-hang Han,et al.  Rhenium-Metalated Polypyridine-Based Porous Polycarbazoles for Visible-Light CO2 Photoreduction , 2019, ACS Catalysis.

[30]  Ping Liu,et al.  Bottom‐Up Preparation of Fully sp2‐Bonded Porous Carbons with High Photoactivities , 2019, Advanced Functional Materials.

[31]  R. Navarro,et al.  Fluorine-Phenanthroimidazole Porous Organic Polymer: Efficient Microwave Synthesis and Photocatalytic Activity. , 2018, ACS applied materials & interfaces.

[32]  Zhimin Liu,et al.  Eosin Y-Functionalized Conjugated Organic Polymers for Visible-Light-Driven CO2 Reduction with H2 O to CO with High Efficiency. , 2018, Angewandte Chemie.

[33]  I. Hermans,et al.  2D Covalent Organic Frameworks as Intrinsic Photocatalysts for Visible Light-Driven CO2 Reduction. , 2018, Journal of the American Chemical Society.

[34]  H. Tian,et al.  Molecular Engineering of Donor–Acceptor Conjugated Polymer/g‐C3N4 Heterostructures for Significantly Enhanced Hydrogen Evolution Under Visible‐Light Irradiation , 2018, Advanced Functional Materials.

[35]  H. Yue,et al.  Visible-Light-Enabled Construction of Thiocarbamates from Isocyanides, Thiols, and Water at Room Temperature. , 2018, Organic letters.

[36]  Zhonghua Xiang,et al.  Ultrastable and Efficient Visible-Light-Driven Hydrogen Production Based on Donor-Acceptor Copolymerized Covalent Organic Polymer. , 2018, ACS applied materials & interfaces.

[37]  Jinghui Zeng,et al.  Dibenzothiophene Dioxide Based Conjugated Microporous Polymers for Visible-Light-Driven Hydrogen Production , 2018, ACS Catalysis.

[38]  Weijie Zhang,et al.  Visible Light-Driven C-3 Functionalization of Indoles over Conjugated Microporous Polymers , 2018, ACS Catalysis.

[39]  Lei Wang,et al.  Asymmetric Covalent Triazine Framework for Enhanced Visible-Light Photoredox Catalysis via Energy Transfer Cascade. , 2018, Angewandte Chemie.

[40]  C. Ochsenfeld,et al.  Tailor‐Made Photoconductive Pyrene‐Based Covalent Organic Frameworks for Visible‐Light Driven Hydrogen Generation , 2018, Advanced Energy Materials.

[41]  Bao-hang Han,et al.  Cationic Polycarbazole Networks as Visible-Light Heterogeneous Photocatalysts for Oxidative Organic Transformations , 2018 .

[42]  Jeehye Byun,et al.  Poly(benzothiadiazoles) and Their Derivatives as Heterogeneous Photocatalysts for Visible-Light-Driven Chemical Transformations , 2018 .

[43]  A. Cooper,et al.  Covalent Triazine Frameworks via a Low‐Temperature Polycondensation Approach , 2017, Angewandte Chemie.

[44]  Bin Liu,et al.  Synthesis of novel ferrocene-based conjugated microporous polymers with intrinsic magnetism , 2017 .

[45]  Bin Liu,et al.  Synthesis of stable metal-containing porous organic polymers for gas storage , 2017 .

[46]  N. Zhang,et al.  Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production. , 2016, Journal of the American Chemical Society.

[47]  David A. Nicewicz,et al.  Organic Photoredox Catalysis. , 2016, Chemical reviews.

[48]  K. Landfester,et al.  Bandgap Engineering of Conjugated Nanoporous Poly-benzobisthiadiazoles via Copolymerization for Enhanced Photocatalytic 1,2,3,4-Tetrahydroquinoline Synthesis under Visible Light , 2016 .

[49]  K. Landfester,et al.  Molecular Structural Design of Conjugated Microporous Poly(Benzooxadiazole) Networks for Enhanced Photocatalytic Activity with Visible Light , 2015, Advanced materials.

[50]  K. Landfester,et al.  Photocatalytic Suzuki Coupling Reaction Using Conjugated Microporous Polymer with Immobilized Palladium Nanoparticles under Visible Light , 2015 .

[51]  Reiner Sebastian Sprick,et al.  Tunable organic photocatalysts for visible-light-driven hydrogen evolution. , 2015, Journal of the American Chemical Society.

[52]  D. MacMillan,et al.  Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. , 2013, Chemical reviews.

[53]  Satoshi Watanabe,et al.  Design principle for increasing charge mobility of π-conjugated polymers using regularly localized molecular orbitals , 2013, Nature Communications.