Micellar catalysis beyond the hydrophobic effect: Efficient palladium catalyzed Suzuki-Miyaura coupling of water and organic solvent insoluble pigments with food grade surfactants

Ceriani, Chiara; Pallini, Francesca; Mezzomo, Lorenzo; Sassi, Mauro; Mattiello, Sara; Beverina, Luca

doi:10.1016/j.jorganchem.2022.122267

Cited by 9 publications

(11 citation statements)

References 79 publications

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Section: Sustainable Reaction Methodsmentioning

confidence: 98%

“…We developed a safe, scalable, and simple procedure requiring the use of an aqueous solution of TL82 as the reaction medium in the absence of any organic solvent. 113 The process proved very efficient on bromides and demonstrated that under the appropriate conditions, surfactant enhanced reactions are efficient on dispersion as much as they are with emulsion and micellar solutions. Our work with pigments represented the missing link we were looking for to carry out efficient polymerizations not only in the absence of organic solvents during synthesis but during processing as well.…”

Section: Accepted Manuscriptmentioning

confidence: 95%

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Polyconjugated Materials for Printed (Opto)Electronics: Introducing Sustainability

Beverina,

Sassi,

Mattiello

et al. 2023

Synlett

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This account summarizes the impact that the quest for sustainability is having on the field of organic polyconjugate molecules and polymers for plastic (opto)electronics. While at the proof-of-concept level, the design criteria as well as the preferred synthetic strategies to access new and improved materials, have been dominated by the need of performance. The ongoing transition from the lab environment to the industrial scale imposes strict limitations to the cost and overall environmental impact of new materials. We here summarize our efforts devoted to the development of new design criteria and synthetic strategies aimed at improving sustainability - without compromising performances - in organic polyconjugated molecules. The article is composed of three sections: Introduction and motivation, sustainability through improved synthetic methods and through improved design. Outline 1 Introduction and motivation 2 Sustainable reaction methods 2.1 The new tools: reactions in aqueous solution of surfactants 2.2 Intrinsically more sustainable reactions: direct arylation 2.3 Sustainable multistep protocols: combining micellar, solventless and mechanochemical methods. 3 Sustainability as a design criterion: de novo design 4 Conclusion

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Section: Sustainable Reaction Methodsmentioning

confidence: 98%

Section: Accepted Manuscriptmentioning

confidence: 95%

Polyconjugated Materials for Printed (Opto)Electronics: Introducing Sustainability

Beverina,

Sassi,

Mattiello

et al. 2023

Synlett

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“…We have recently shown that lecithin gives homogeneous dispersion of organic solids in water and makes it possible to efficiently carrying out SM reactions without dissolving the reagents. [57,62] Under such conditions, the formation of an interpenetrating polymeric network would be prevented as the solid monomers are never dissolved, but slowly etched at the surface by the action of the dispersant. Prior to proceed with the polymerization, we optimized the reaction conditions on small molecule model compounds-as discussed in Supporting Information-confirming that TL82 is at least as efficient as the previously employed mixture of K-EL 2 wt% in water in the presence of 10 vol% toluene.…”

Section: Polymerization Reactions and Purification Protocolsmentioning

confidence: 99%

“…Indeed, we demonstrated that almost insoluble halogenated organic pigments can be efficiently coupled with a variety of boronic acids while dispersed in a TL82 aqueous mixture. [ 62 ] We here show that TL82 can be successfully used for the preparation of high molecular weight semiconducting polymers, where conversion of the growing oligomers in insoluble solids is expected to happen. The reaction is more efficient and purification becomes straightforward thus further improving the appeal of the method.…”

Section: Introductionmentioning

confidence: 96%

Organic Solvent Free Synthesis and Processing of Semiconducting Polymers for Field Effect Transistors in Waterborne Dispersions

Ceriani

Scagliotti

Losi

et al. 2023

Adv Elect Materials

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Conjugated semiconducting polymers are key active materials for printable electronics, sensors and biosensors, organic photovoltaics, organic light emitting devices, and more. The research in the field developed very efficient materials and sound structure property relationships, thus making a case for a transition from laboratory to industrial environment. At this critical juncture, sustainability, and ease of scaling up are at least as important as performances, to the point that efficient materials on a lab scale could become unpractical for the industry. The development of more efficient synthetic protocols and the complete removal of all organic solvents from both the synthesis and the processing of semiconducting polymers can help tremendously to improve sustainability and reduce costs. It is shown that the use of an aqueous dispersion of the food grade surfactant lecithin as the medium, enables the synthesis and processing of the representative semiconducting alternating copolymer poly (9,9‐dioctylfluorene‐alt‐bithiophene) (PF8T2) in high yield and high quality and with transistor performances comparable with those obtained with reference materials synthetized and processed from volatile organic solvents.

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“…Aqueous surfactant mixtures provide a promising sustainable approach for performing organic reactions in water instead of in organic solvents. Recently, applications of this approach have been developed in both academic − and industrial settings, ,− including on scale, encompassing a range of modern synthetic reactions (e.g., oxidative addition to metal powders, palladium-catalyzed cross-coupling, ,,− amination, , and sulfonations). Yet, optimization of these surfactant-based reaction systems remains largely screening-based, including selection of which surfactants and concentrations in each component.…”

Section: Introductionmentioning

confidence: 99%

Surfactant Micellar and Vesicle Microenvironments and Structures under Synthetic Organic Conditions

Peacock

Blum

2023

J. Am. Chem. Soc.

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Fluorescence lifetime imaging microscopy (FLIM) reveals vesicle sizes, structures, microenvironments, reagent partitioning, and system evolution with two chemical reactions for widely used surfactant–water systems under conditions relevant to organic synthesis, including during steps of Negishi cross-coupling reactions. In contrast to previous investigations, the present experiments characterize surfactant systems with representative organohalide substrates at high concentrations (0.5 M) that are reflective of the preparative-scale organic reactions performed and reported in water. In the presence of representative organic substrates, 2-iodoethylbenzene and 2-bromo-6-methoxypyridine, micelles swell into emulsion droplets that are up to 20 μm in diameter, which is 3–4 orders of magnitude larger than previously measured in the absence of an organic substrate (5–200 nm). The partitioning of reagents in these systems is imaged through FLIMdemonstrated here with nonpolar, amphiphilic, organic, basic, and oxidative-addition reactive compounds, a reactive zinc metal powder, and a palladium catalyst. FLIM characterizes the chemical species and/or provides microenvironment information inside micelles and vesicles. These data show that surfactants cause surfactant-dictated microenvironments inside smaller micelles (<200 nm) but that addition of a representative organic substrate produces internal microenvironments dictated primarily by the substrate rather than by the surfactant, concurrent with swelling. Addition of a palladium catalyst causes the internal environments to differ between vesiclesinformation that is not available through nor predicted from prior analytical techniques. Together, these data provide immediately actionable information for revising reaction models of surfactant–water systems that underpin the development of sustainable organic chemistry in water.

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Micellar catalysis beyond the hydrophobic effect: Efficient palladium catalyzed Suzuki-Miyaura coupling of water and organic solvent insoluble pigments with food grade surfactants

Cited by 9 publications

References 79 publications

Polyconjugated Materials for Printed (Opto)Electronics: Introducing Sustainability

Polyconjugated Materials for Printed (Opto)Electronics: Introducing Sustainability

Organic Solvent Free Synthesis and Processing of Semiconducting Polymers for Field Effect Transistors in Waterborne Dispersions

Surfactant Micellar and Vesicle Microenvironments and Structures under Synthetic Organic Conditions

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