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

Simply Complex: The Efficient Synthesis of an Intricate Molecular Acceptor for High-Performance Air-Processed and Air-Tested Fullerene-Free Organic Solar Cells DOI
Seth M. McAfee, Sergey Dayneko, Pierre Josse

et al.

Chemistry of Materials, Journal Year: 2017, Volume and Issue: 29(3), P. 1309 - 1314

Published: Jan. 7, 2017

A perylene diimide (PDI) flanked diketopyrrolopyrrole (DPP) π-conjugated small molecule has been synthesized through an efficient and sustainable direct heteroarylation protocol. When paired with the donor polymer PTB7-Th, air-processed tested bulk-heterojunction (BHJ) organic solar cells (OSCs) achieved a high power conversion efficiency (PCE) of 5.6%. The new acceptor showed favorable morphological changes upon solvent vapor annealing leading to near 3-fold increase in PCE. This result is among best reported utilizing DPP-based acceptors OSCs. All exhibited good air light stability over 35-day evaluation period.

Language: Английский

Citations

105
Manganese‐Catalyzed C−H Alkynylation: Expedient Peptide Synthesis and Modification DOI
Zhixiong Ruan,

Nicolas Sauermann,

Elisabetta Manoni

et al.

Angewandte Chemie, Journal Year: 2017, Volume and Issue: 129(12), P. 3220 - 3224

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

105
Biomass-Derived Solvents for Sustainable Transition Metal-Catalyzed C–H Activation DOI
Parthasarathy Gandeepan, Nikolaos Kaplaneris, Stefano Santoro

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2019, Volume and Issue: 7(9), P. 8023 - 8040

Published: March 29, 2019

Transition metal-catalyzed C–H activation has emerged as an increasingly powerful strategy in molecular syntheses and a particularly attractive alternative to classical methods of cross-couplings. During the recent years, significant focus been dedicated further improve sustainable nature approach. As solvents represent major portion organic pollution caused by chemical syntheses, range nontoxic, biobased, have developed substitute for common reaction media. In this review, we present general perspective biomass-derived transition reactions their unique potential up January 2019.

Language: Английский

Citations

100
Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis DOI
Torben Rogge, João C. A. Oliveira, Rositha Kuniyil

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10551 - 10558

Published: Aug. 17, 2020

Detailed density functional theory calculations provide valuable insight into reactivity-controlling factors in transition metal-catalyzed C–H activation by carboxylate assistance. The chelation-assisted of a variety arenes 3d and 4d metal complexes was analyzed means bond order analysis through (DFT) as well energy decomposition DLPNO–CCSD(T) calculations, thereby providing in-depth information on distinct electronic influences the key state demonstrating preferred base-assisted internal electrophilic substitution (BIES) rather than concerted metalation-deprotonation (CMD) pathway.

Language: Английский

Citations

93
Challenges to the Success of Commercial Organic Photovoltaic Products DOI
Maximilian Moser, Andrew Wadsworth, Nicola Gasparini

et al.

Advanced Energy Materials, Journal Year: 2021, Volume and Issue: 11(18)

Published: March 24, 2021

Abstract Recent advances in the development of organic photovoltaic (OPV) materials has led to significant improvements device performance; now closing on 20% efficiency threshold. Despite these performance, commercial viability products remains elusive. In this perspective, current limitations high performing blends are uncovered, particularly focusing industrial upscaling considerations materials, such as synthetic scalability, active layer processing, and stability. Moreover, a simplified metric, namely, scalability factor (SF), is introduced evaluate scale‐up potential specific OPV thereof. Of most popular molecular design strategies investigated recent times, it found that use Y‐series nonfullerene acceptors (NFAs) synthetically simple PTQ‐10 ternary blends, effective at maximizing without negatively impacting SF. Furthermore, needed, terms processability stability, considered for final product application. Finally, an outlook photovoltaics provided both from perspective important research avenues applications can be exploited.

Language: Английский

Citations

92
Metal Coordination Complexes as Redox Mediators in Regenerative Dye-Sensitized Solar Cells DOI Creative Commons
Yasemin Saygılı, Marko Stojanović, Natalie Flores‐Díaz

et al.

Inorganics, Journal Year: 2019, Volume and Issue: 7(3), P. 30 - 30

Published: Feb. 26, 2019

Dye-sensitized solar cells (DSSCs) have attracted a substantial interest in the last 30 years for conversion of power to electricity. An important component is redox mediator effecting transport charge between photoelectrode and dark counter electrode (CE). Among possible mediators, metal coordination complexes play prominent role at present are incorporated several types devices with efficiency exceeding 10%. The review, after brief introduction operation DSSCs, discusses first requirements successful mediator. Subsequently, properties various classes inorganic functioning as mediators relevant DSSC presented operational characteristics analyzed. Particular emphasis paid two main efficient cobalt copper; however other less but promising notably iron, nickel, manganese vanadium, also presented.

Language: Английский

Citations

90
C–H activation derived CPPs for photocatalytic hydrogen production excellently accelerated by a DMF cosolvent DOI
Weiya Huang,

Zhao‐Qi Shen,

Jing-Zhao Cheng

et al.

Journal of Materials Chemistry A, Journal Year: 2019, Volume and Issue: 7(42), P. 24222 - 24230

Published: Jan. 1, 2019

An atom-economic synthetic method is developed to access CPP materials used for photocatalytic H2 production from H2O, and the PHP reaction can be greatly accelerated by DMF cosolvent, leading an HER of 15 975 μmol g−1 h−1 without aid Pt.

Language: Английский

Citations

87
Conjugated and Conducting Organic Polymers: The First 150 Years DOI
Seth C. Rasmussen

ChemPlusChem, Journal Year: 2020, Volume and Issue: 85(7), P. 1412 - 1429

Published: July 1, 2020

Abstract Conductive organic polymers are most commonly generated from the oxidation or reduction of conjugated polymers. Although such typically viewed as modern materials, earliest examples these date back to early 19th century. The era began with first reports their conductive nature in 1960s. However, it was advances 1970s that brought particular focus materials example conductivity values metallic regime, for which 2000 Nobel Prize Chemistry awarded Hideki Shirakawa, Alan MacDiarmid, and Heeger. Unfortunately, historical narrative is currently quite muddled primary literature, various inaccuracies propagated. In an effort present a more accurate account resource field, report will review 150 years four parent polymers−polyaniline, polypyrrole, polyacetylene, polythiophene, origins 1834 rapid development mid‐1980s.

Language: Английский

Citations

85
Semiconducting Polymers Based on Isoindigo and Its Derivatives: Synthetic Tactics, Structural Modifications, and Applications DOI

Xuyang Wei,

Weifeng Zhang, Gui Yu

et al.

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(21)

Published: March 5, 2021

Abstract The past few decades have witnessed the tremendous development of semiconducting polymers in electronic applications, which is inextricably related to diversity polymer structure. change structure significantly influences packing, thin film morphology, and other optoelectronic properties, thus meeting need for different device applications. With synthetic chemistry theoretical computation, many high‐performance building blocks emerged. Among them, isoindigo‐ isoindigo derivatives‐based are widely studied various fields organic electronics, them showed excellent properties. This review summarizes tactics isoindigo‐derived monomers polymers. Moreover, structural modification strategies discussed detail, including derivatives regulation type. Using polymers, such as field‐effect transistors, chemical sensors, electrochemical phototransistors, photovoltaics, thermoelectrics, spin valves, biophotonic introduced illustrate important effects modification.

Language: Английский

Citations

80
Significant Difference in Semiconducting Properties of Isomeric All‐Acceptor Polymers Synthesized via Direct Arylation Polycondensation DOI
Yang Wang, Tsukasa Hasegawa, Hidetoshi Matsumoto

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(34), P. 11893 - 11902

Published: June 18, 2019

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups the reactive carbon-hydrogen (C-H) bonds, which limits choice of units. In this study, we describe a DArP high-molecular-weight all-acceptor composed without any via modified using Pd/Cu co-catalysts. We thus obtained two isomeric polymers, P1 and P2, have same backbone side-chains different positions nitrogen atoms in thiazole This subtle change significantly influences their optoelectronic, molecular packing, charge-transport properties. P2 greater torsion has favorable edge-on orientations high electron mobility μe 2.55 cm2 V-1 s-1 . Moreover, P2-based transistors show excellent shelf-storage stability air even after storage 1 month.

Language: Английский

Citations

79