Advances in applying C–H functionalization and naturally sourced building blocks in organic semiconductor synthesis

Xing, Liwen; Luscombe, Christine K.

doi:10.1039/d1tc04128b

Cited by 26 publications

(21 citation statements)

References 163 publications

(256 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Specifically, the metal catalysts typically are not sufficiently selective to distinguish between the electron-rich and electron-poor monomers, which leads to homocoupling defects in the D–A polymer products . Thus far, limited progress has been made in this field. ,− …”

Section: Introductionmentioning

confidence: 99%

An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization

et al. 2022

Self Cite

View full text Add to dashboard Cite

The Carothers equation is often used to predict the utility of a small molecule reaction in a polymerization. In this study, we present the mechanistic study of Pd/Ag cocatalyzed cross dehydrogenative coupling (CDC) polymerization to synthesize a donor−acceptor (D−A) polymer of 3,3′-dihexyl-2,2′-bithiophene and 2,2′,3,3′,5,5′,6,6′-octafluorobiphenyl, which go counter to the Carothers equation. It is uncovered that the second chain extension cross-coupling proceeds much more efficiently than the first crosscoupling and the homocoupling side reaction (at least 1 order of magnitude faster) leading to unexpectedly low homocoupling defects and high molecular weight polymers. Kinetic analyses show that C−H bond activation is rate-determining in the first crosscoupling but not in the second cross-coupling. Based on DFT calculations, the high cross-coupling rate in the second cross-coupling was ascribed to the strong Pd-thiophene interaction in the Pdmediated C−H bond activation transition state, which decreases the energy barrier of the Pd-mediated C−H bond activation. These results have implications beyond polymerizations and can be used to ease the synthesis of a wide range of molecules where C−H bond activation may be the limiting factor.

show abstract

Section: Introductionmentioning

confidence: 99%

An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…58 Indeed, a vast library of conjugated polymers prepared by direct heteroarylation po-lymerization (DArP) can be found in the literature, with properties comparable to those of conventional polymerization methods. 59 Though small molecule arylation methodologies became the springboard for polymerization studies, only one example of DArP performed at room temperature is known in the literature. In 2020, the Luscombe group successfully demonstrated the polymerization of indole at room temperature 60 by adapting the protocol developed by the Larrosa group for small-molecule synthesis 30 at room temperature.…”

Section: Direct Arylation Polymerizationmentioning

confidence: 99%

Recent Advances in Room-Temperature Direct C–H Arylation Methodologies

Yadav¹,

Velmurugan²,

Luscombe³

2022

Synthesis

Self Cite

View full text Add to dashboard Cite

In recent decades, direct C-H arylation has become a preferred tool for biaryl coupling over traditional cross-coupling methods owing to its operationally simple protocol, inherent atom and step economy, and reduced metallic waste. Several elegant methods have been developed that offer the facile transformation of usually inert Csp2-H bonds to Csp2-Csp2 bonds in a single synthetic operation. Despite many merits, a major drawback to this chemistry comes from aryl-C-H bonds' low reactivity, which often mandate harsh reaction conditions compromising sustainability. Hence, developing reaction protocols that require milder conditions has become an important goal in this area of research. This review article comprehensively highlights the synthesis and mechanistic aspects of direct C-H arylation reactions, which proceed at or below room temperature.

show abstract

“…Conjugated polymers (CPs) provide low-cost, scalable, and mechanically robust alternatives to many inorganic semiconductors for numerous electronics applications, including thin-film transistors, (bio)chemical sensors, displays, and photovoltaics. − A central enabling feature of CPs is the ability to readily modulate the physical and electronic properties through structural modifications, such as varying the alkyl substituents or functionalization of the conjugated backbone. − Thus, simple structural modification of the repeating units can have profound effects on the chemical and physical properties of the corresponding polymer. An example of this strategy is the incorporation of amide and imide functionalities into arene and heteroarene scaffolds as exemplified by the structures shown in Figure A. , These moieties imbue desirable morphological and charge transport properties without involving arduous synthetic pathways that can increase material costs and diminish the sustainable aspects of organic optoelectronics. − As an example, the polymer acceptor, N2200 (Figure A), provides considerable power conversion efficiencies (PCEs) in all-polymer solar cells (APSCs) without the need for extensive structural modifications and synthetic complexity. − In fact, optimization of the donor polymer structure ( e.g. , PTzBI-Si ) (Figure C) and the active layer morphology (processing the polymer blend using cyclopentyl methyl ether [CPME]) for APSCs incorporating N2200 has enabled PCEs approaching 11% .…”

Section: Introductionmentioning

confidence: 99%

All-Polymer Solar Cells Incorporating Readily Accessible Naphthalene Diimide and Isoindigo Acceptor Polymers for Improved Light Harvesting

Pankow

Harbuzaru

et al. 2022

Chem. Mater.

View full text Add to dashboard Cite

The development of readily accessible polymer acceptors is imperative to preserve the guiding principles of all-polymer solar cells as a low-cost and sustainable technology for alternative energy production. In this study, we report a computationally guided design and facile synthesis of new acceptor polymers comprising the alternating copolymer, PNIT, and the corresponding random copolymer, r-PNIT, which incorporate structurally simple naphthalene diimide (NDI) and isoindigo (IID) units. PNIT was prepared via direct arylation polymerization (DArP), which proceeds via C–H activation and avoids the use of toxic reagents and extended synthetic pathways for the monomer synthesis. PNIT has broad optical absorption in the 300–850 nm range and an enhanced absorption coefficient (47 × 103 cm–1) compared to r-PNIT (300–850 nm; 40 × 103 cm–1). When incorporated in all-polymer solar cells (APSCs) using PBDB-T as the donor polymer, PBDB-T:PNIT provides greater than two times the average (maximum) power conversion efficiency (PCE) of 5.18 ± 0.08 (5.32)% compared to that of PBDB-T:r-PNIT, 2.38 ± 0.16 (2.57)%, due to increased J sc (10.36 vs 5.45 mA cm–2) and fill factor (FF) (0.58 vs 0.50) metrics. The PBDB-T:PNIT PCE is among the highest reported for an IID-based APSC and demonstrates the viability of DArP for the synthesis of new APSC acceptor polymers. Detailed morphological and microstructural investigations using atomic force microscopy (AFM) and grazing-incidence wide-angle X-ray scattering (GIWAXS), respectively, reveal enhanced texturing for PNIT, which enhances charge transport properties as supported by space-charge-limited current (SCLC) mobility measurements.

show abstract

Advances in applying C–H functionalization and naturally sourced building blocks in organic semiconductor synthesis

Abstract: This review presents the recent advances in the synthesis of organic semiconductors using C–H functionalization and naturally sourced building blocks to facilitate the large-scale production and commercialization of organic semiconductors.

Cited by 26 publications

References 163 publications

An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization

An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization

Recent Advances in Room-Temperature Direct C–H Arylation Methodologies

All-Polymer Solar Cells Incorporating Readily Accessible Naphthalene Diimide and Isoindigo Acceptor Polymers for Improved Light Harvesting

Contact Info

Product

Resources

About