Influence of an ester directing-group on defect formation in the synthesis of conjugated polymers <i>via</i> direct arylation polymerization (DArP) using sustainable solvents

Pankow, Robert M.; Ye, Liwei; Thompson, Barry C.

doi:10.1039/c9py00815b

Cited by 28 publications

(48 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…By contrast, the polymerization reaction of 1 with thieno[3,4- b ][1,4]dioxine mainly yielded an insoluble solid in common organic solvents, and only a small number of products can be isolated by Soxhlet extractions with CHCl 3 to provide a total yield of about 10%. This result may be due to the cross-linking reaction in multiple C-H systems [ 30 , 31 ]. Dithienosilole cores are common building blocks of various active materials used in photovoltaics, FETs, and OLEDs, etc.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of π-Conjugated Polymers Containing Benzotriazole Units via Palladium-Catalyzed Direct C-H Cross-Coupling Polycondensation for OLEDs Applications

Han

Zhang

et al. 2021

Polymers

View full text Add to dashboard Cite

Four D-π-A conjugated polymers, namely P1–P4, which contain benzotriazole building blocks in their backbone as acceptor, are synthesized via palladium-catalyzed direct C-H cross-coupling polycondensation of 5,6-difluorobenzotriazole with different thiophene derivatives, including 3-octylthiophene, 2,2’-bithiophene, thieno[3,4-b][1,4]dioxine, and 4,4-dioctyl-4H-silolo-[3,2-b:4,5-b’]dithiophene as donor units, respectively. Taking the polymer P1 as an example, the chemical structure of the polymer is demonstrated by 1H and 19F NMR spectra. The optical, electrochemical, and thermal properties of these polymers are assessed by UV–vis absorption and fluorescence spectroscopy, cyclic voltammetry (CV), and thermal gravimetric analysis (TGA), respectively. DFT simulations of all polymers are also performed to understand their physicochemical properties. Furthermore, P1 and P2, which have relatively higher molecular weights and better fluorescent quantum efficiency than those of P3 and P4, are utilized as lighting emitters for organic light-emitting diodes (OLEDs), affording promising green and red luminescence with 0.07% and 0.14% of maximum external quantum efficiency, respectively, based on a device with an architecture of ITO/PEDOT:PSS/PTAA/the polymer emitting layer/TPBi/LiF/Al.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of π-Conjugated Polymers Containing Benzotriazole Units via Palladium-Catalyzed Direct C-H Cross-Coupling Polycondensation for OLEDs Applications

Han

Zhang

et al. 2021

Polymers

View full text Add to dashboard Cite

show abstract

“…[ 17 ] Notwithstanding CPME is currently synthesized by petrochemical derivatives with a high atom economy, its production could also involve natural substrates, such as furfural or adipic acid. [ 18 ] To the best of our knowledge, however, few are the cases concerning the use of CPME [ 19–22 ] as well as of other green solvents (especially, 2‐MeTHF) [ 23–25 ] as a sustainable medium for the synthesis of conjugated polymers via DArP.…”

Section: Introductionmentioning

confidence: 99%

Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent

Conelli

Grisorio

Suranna

2020

Macro Chemistry & Physics

View full text Add to dashboard Cite

Direct arylation polymerization (DArP) relieves the synthesis of conjugated polymers from the use of hazardous and toxic reagents typical of the traditional protocols. However, the compatibility with environmentally benign, nonhazardous, and low‐cost solvents still represents the critical aspect for projecting DArP as an industrial‐scale method for the preparation of conjugated polymers. In this study, a “green” solvent (i.e., cyclopentyl methyl ether) is implemented for the obtainment of poly(3‐hexylthiophene) by DArP reaction, in order to explore sustainable reaction conditions also regarding the catalytic system and the base quantity, which equally undermine the sustainability of the DArP protocol. Considering the molecular weights as the indicator of precatalyst performance in determined conditions, it is established that the cheapest palladium source (i.e., PdCl2) combined with two equivalents of (o‐anisyl)3P is able to yield the best results in the green ethereal solvent. Furthermore, it is found how, with respect to the common DArP protocols, the quantity of the expensive base (i.e., Cs2CO3) can be reduced in these reaction conditions without compromising molecular weights and regioregularity of the resulting polymer. These optimized reaction conditions can be extended to the copolymerization of other monomer units with satisfactory results in terms of molecular weights.

show abstract

“…In 2019, Thompson's group reported the DArP of a thiophene derivative with an ester derivative in cyclopentyl methyl ether solvent (Scheme 4a). [34] The reaction was complete in less than Scheme 3. Different reaction conditions used in the DArP of thiophene derivatives.…”

Section: Poly(thiophenes)mentioning

confidence: 98%

“…The directing group serves both to increase reactivity and to improve regioselectivity of the reaction. In 2019, Thompson's group reported the DArP of a thiophene derivative with an ester derivative in cyclopentyl methyl ether solvent (Scheme 4a) [34] . The reaction was complete in less than 1 hour, forming A2 with a yield of 59% and an M n of 14 kg/mol.…”

Section: Direct Arylation Polymerization (Darp)mentioning

confidence: 99%

Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Chua

Png

Zhu

et al. 2021

Chemistry An Asian Journal

View full text Add to dashboard Cite

Transition metal catalysed CÀ H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of CÀ C bonds in the construction of piconjugated systems, particularly for conjugated polymers, has benefited much from the advances in CÀ H bond activation chemistry. Compared to conventional transitionmetal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve CÀ H/CÀ X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves CÀ H/CÀ H cross-coupling protocols driven by the activation of monomers' C(sp 2 )À H bonds. Furthermore, poly(annulation) via CÀ H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed CÀ H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno [3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrolecontaining copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed CÀ H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed CÀ H activation polymerization to prepare conjugated polymers were discussed and commented.

show abstract

Influence of an ester directing-group on defect formation in the synthesis of conjugated polymers via direct arylation polymerization (DArP) using sustainable solvents

Abstract: We report the application of green solvents in DArP and the structure-dependent β-defect formation due to an ester directing group.

Cited by 28 publications

References 77 publications

Synthesis of π-Conjugated Polymers Containing Benzotriazole Units via Palladium-Catalyzed Direct C-H Cross-Coupling Polycondensation for OLEDs Applications

Synthesis of π-Conjugated Polymers Containing Benzotriazole Units via Palladium-Catalyzed Direct C-H Cross-Coupling Polycondensation for OLEDs Applications

Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent

Synthesis of Conjugated Polymers via Transition Metal Catalysed C−H Bond Activation

Contact Info

Product

Resources

About