A High‐Performance n‐Type Thermoelectric Polymer from C−H/C−H Oxidative Direct Arylation Polycondensation DOI
Yibo Shi, Xuwen Zhang, Tian Du

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 14, 2023

Abstract n‐Type conjugated polymers (CPs) are crucial in the applications of organic electronics. Direct coupling electron‐deficient C−H monomer via selective activation, namely C−H/C−H oxidative direct arylation polycondensation (Oxi‐DArP), is an ideal approach toward such CPs. Herein, Oxi‐DArP firstly adopted to synthesize a high‐performance n‐type CP using newly developed monomer, i.e., 3,6‐di(thiazol‐5‐yl)‐diketopyrrolopyrrole (Tz‐5‐DPP). Tz‐5‐DPP based homopolymer PTz ‐ 5 DPP with molecular weight 22 kDa has been synthesized Oxi‐DArP. After n‐doping, films exhibited electric conductivity values up 8 S cm −1 and power factors ( PFs ) 106 μW m K −2 . Notably, this PF value highest for polymer thermoelectric materials date. The synthesis excellent performance make work important step straightforward sustainable preparation semiconductors.

Language: Английский

The Green ChemisTREE: 20 years after taking root with the 12 principles DOI
Hanno C. Erythropel, Julie B. Zimmerman,

Tamara M. de Winter

et al.

Green Chemistry, Journal Year: 2018, Volume and Issue: 20(9), P. 1929 - 1961

Published: Jan. 1, 2018

A broad overview of the achievements and emerging areas in field Green Chemistry.

Language: Английский

Citations

637
Direct (Hetero)arylation Polymerization: Simplicity for Conjugated Polymer Synthesis DOI

Jean‐Rémi Pouliot,

François Grenier,

J. Terence Blaskovits

et al.

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(22), P. 14225 - 14274

Published: Nov. 3, 2016

Direct (hetero)arylation polymerization (DHAP) has recently been established as an environmentally benign method for the preparation of conjugated polymers. This synthetic tool features formation C-C bonds between halogenated (hetero)arenes and simple with active C-H bonds, thereby circumventing organometallic derivatives decreasing overall production cost Since its inception, selectivity reactivity DHAP procedures have improved tremendously through careful scrutinity outcomes fine-tuning reaction conditions. A broad range monomers, from arenes to complex functionalized heteroarenes, can now be readily polymerized. The successful application leads nearly defect-free polymers possessing comparable, if not slightly better, characteristics than their counterparts prepared using classical cross-coupling methods. comprehensive review describes mechanisms involved in this process experimental theoretical standpoints, presents up-to-date compendium materials obtained by means, exposes current limitations challenges.

Language: Английский

Citations

455
Manganese‐Catalyzed C−H Alkynylation: Expedient Peptide Synthesis and Modification DOI
Zhixiong Ruan,

Nicolas Sauermann,

Elisabetta Manoni

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(12), P. 3172 - 3176

Published: Feb. 9, 2017

Abstract Manganese(I)‐catalyzed C−H alkynylations with organic halides occurred unparalleled substrate scope, and thus enabled step‐economical functionalizations silyl, aryl, alkenyl, alkyl haloalkynes. The versatility of the manganese(I) catalysis manifold couplings haloalkynes featuring, among others, fluorescent labels, steroids, amino acids, thereby setting stage for peptide ligation as well efficient molecular assembly acyclic cyclic peptides. A plausible catalytic cycle was proposed.

Language: Английский

Citations

278
Tin-Free Direct C–H Arylation Polymerization for High Photovoltaic Efficiency Conjugated Copolymers DOI
Alexander S. Dudnik, Thomas J. Aldrich,

Nicholas D. Eastham

et al.

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(48), P. 15699 - 15709

Published: Nov. 9, 2016

A new and highly regioselective direct C–H arylation polymerization (DARP) methodology enables the reproducible sustainable synthesis of high-performance π-conjugated photovoltaic copolymers. Unlike traditional Stille polycondensation methods for producing copolymers, this DARP protocol eliminates need environmentally harmful, toxic organotin compounds. This employs low loadings commercially available catalyst components, Pd2(dba)3·CHCl3 (0.5 mol%) P(2-MeOPh)3 (2 mol%), sterically tuned carboxylic acid additives, an friendly solvent, 2-methyltetrahydrofuran. Using protocol, several representative copolymers are synthesized in excellent yields high molecular masses. The DARP-derived benchmarked versus Stille-derived counterparts by close comparison optical, NMR spectroscopic, electrochemical properties, all which indicate great chemical similarity no significant detectable structural defects DARP- copolymer fullerene blend microstructural properties morphologies characterized with AFM, TEM, XRD found to be virtually indistinguishable. Likewise, charge generation, recombination, transport characteristics films identical. For first time, polymer solar cells fabricated using exhibit cell performances rivalling or exceeding those achieved materials. PBDTT-FTTE, power conversion efficiency 8.4% is a record copolymer.

Language: Английский

Citations

172
Reductive Functionalization of Pyridine-Fused N-Heteroarenes DOI
Huanhuan Jia, Zhenda Tan, Min Zhang

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 795 - 813

Published: Feb. 23, 2024

ConspectusThe selective functionalization/transformation of ubiquitous pyridine-fused N-heteroarenes is a practical method to synthesize structurally novel N-heterocycles, which important for the development medicines, bioactive agents, agrochemicals, materials, ligands, sensors, pigments, dyes, etc. However, owing thermodynamic stability, kinetic inertness, and lone electron pair–induced catalyst deactivation N-heteroarenes, limited strategies (e.g., C–H activation/functionalization, electrophilic substitution, Minisci reaction) are available realize synthetic purpose maintain aromaticity final products. Moreover, relevant transformations have limitations such as needing harsh reaction conditions, requiring preinstallation specific coupling agents containing transformable functionalities or directing groups, using less environmentally benign oxidants and/or acidic activators, poor selectivity. Herein, considering that imines, enamines, radicals, cyclic amines generated during reduction precise transformation these reductive intermediates offers fundamental basis developing tandem reactions. Our group revealed slow rate, synergistic catalysis, controlled electroreduction effective fulfilling functionalization N-heteroarenes. Thus, we established series new methods provide diverse construction modalities functionalized N-heterocycles. The striking features include high efficiency, atom economy, use readily accessible feedstocks in absence flammable pressurized H2 gas, alongside promising potential obtained N-heterocyclic present study would be appealing fields organic chemistry, biomedical functional materials. This Account describes application dearomatization substrate-activating reaction-initiating modes summarizes via alkylation, arylation, annulation at nitrogen, α, β, other remote carbon sites achieved over past 8 years. Details regarding reactions their plausible mechanisms perspectives discussed. We hope our contributions this field will aid further tackle intractable challenges area.

Language: Английский

Citations

16
Direct C–H arylation: a “Greener” approach towards facile synthesis of organic semiconducting molecules and polymers DOI
Hassan Bohra, Mingfeng Wang

Journal of Materials Chemistry A, Journal Year: 2017, Volume and Issue: 5(23), P. 11550 - 11571

Published: Jan. 1, 2017

Direct C–H arylation enables “greener” synthesis of π-conjugated small molecules and polymers without tedious preactivation bonds.

Language: Английский

Citations

154
Direct arylation polymerization: A guide to optimal conditions for effective conjugated polymers DOI Creative Commons

Nemal S. Gobalasingham,

Barry C. Thompson

Progress in Polymer Science, Journal Year: 2018, Volume and Issue: 83, P. 135 - 201

Published: June 12, 2018

Language: Английский

Citations

134
meta‐C−H Bromination on Purine Bases by Heterogeneous Ruthenium Catalysis DOI
Svenja Warratz, David Burns, Cuiju Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(6), P. 1557 - 1560

Published: Jan. 3, 2017

Abstract Methods for positionally selective remote C−H functionalizations are in high demand. Herein, we disclose the first heterogeneous ruthenium catalyst meta ‐selective functionalizations, which enabled halogenations with excellent site selectivity and ample scope. The versatile Ru@SiO 2 was broadly applicable could be easily recovered reused, set stage direct fluorescent labeling of purines. In contrast to palladium, rhodium, iridium, or cobalt complexes, solely catalysis manifold provided access ‐halogenated purine derivatives, illustrating unique power activation catalysis.

Language: Английский

Citations

130
Design and effective synthesis methods for high-performance polymer semiconductors in organic field-effect transistors DOI

Longxian Shi,

Yunlong Guo, Wenping Hu

et al.

Materials Chemistry Frontiers, Journal Year: 2017, Volume and Issue: 1(12), P. 2423 - 2456

Published: Jan. 1, 2017

Design and effective synthesis methods for high-performance polymer semiconductor-based OFETs.

Language: Английский

Citations

121
Design strategies of n-type conjugated polymers for organic thin-film transistors DOI
Ying Sui, Yunfeng Deng, Tian Du

et al.

Materials Chemistry Frontiers, Journal Year: 2019, Volume and Issue: 3(10), P. 1932 - 1951

Published: Jan. 1, 2019

Four molecule design strategies of n-type conjugated polymers for organic thin-film transistors are summarized and discussed.

Language: Английский

Citations

114