Computational design of next generation atom transfer radical polymerization ligands

Stewart, Madeleine; Yu, Li‐Juan; Sherburn, Michael S.; Coote, Michelle L.

doi:10.1039/d1py01716k

Cited by 7 publications

(5 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, the synthesis of these ligands is not trivial. The replacement of a methylene group in the quinuclidine cap with an oxygen could offer an easier synthetic pathway without compromising the activity of the resulting Cu catalyst …”

Section: Activity and Selectivity Of Atrp Catalystsmentioning

confidence: 99%

“…The replacement of a methylene group in the quinuclidine cap with an oxygen could offer an easier synthetic pathway without compromising the activity of the resulting Cu catalyst. 39 According to computational data, these rigidified Cu complexes can unlock the ATRP of less activated monomers such as vinyl acetate (VAc), N-vinylpyrrolidone, and Nvinylformamide. K ATRP values correlate to the free energy of C−X bond dissociation (BDFE) in RX initiators mimicking dormant species.…”

Section: Activity and Selectivity Of Atrp Catalystsmentioning

confidence: 99%

See 1 more Smart Citation

Atom Transfer Radical Polymerization: A Mechanistic Perspective

2022

View full text Add to dashboard Cite

Since its inception, atom transfer radical polymerization (ATRP) has seen continuous evolution in terms of the design of the catalyst and reaction conditions; today, it is one of the most useful techniques to prepare well-defined polymers as well as one of the most notable examples of catalysis in polymer chemistry. This Perspective highlights fundamental advances in the design of ATRP reactions and catalysts, focusing on the crucial role that mechanistic studies play in understanding, rationalizing, and predicting polymerization outcomes. A critical summary of traditional ATRP systems is provided first; we then focus on the most recent developments to improve catalyst selectivity, control polymerizations via external stimuli, and employ new photochemical or dual catalytic systems with an outlook to future research directions and open challenges.

show abstract

Section: Activity and Selectivity Of Atrp Catalystsmentioning

confidence: 99%

Section: Activity and Selectivity Of Atrp Catalystsmentioning

confidence: 99%

Atom Transfer Radical Polymerization: A Mechanistic Perspective

2022

View full text Add to dashboard Cite

show abstract

“…ATRP in particular has attracted considerable attention in the last decade aiming to diminish the catalyst concentration without compromising the control over the molar mass distributions 17,21–24 . The use of ppm concentrations of catalysts not only enables a “greener” ATRP process but also significantly minimizes the need for extensive purification 21,25,26 . In addition, the vast majority of these approaches start with the rather stable deactivator (e.g., Cu(II)Br) and rely on the in ‐ situ reduction of Cu(II)Br to Cu(I)Br through various external stimuli 27–29 .…”

Section: Introductionmentioning

confidence: 99%

“…17,[21][22][23][24] The use of ppm concentrations of catalysts not only enables a "greener" ATRP process but also significantly minimizes the need for extensive purification. 21,25,26 In addition, the vast majority of these approaches start with the rather stable deactivator (e.g., Cu(II)Br) and rely on the in-situ reduction of Cu(II)Br to Cu(I)Br through various external stimuli. [27][28][29] For instance, activators regenerated by electron transfer (ARGET) ATRP utilizes a chemical stimulus, typically a reducing agent such as ascorbic acid, to continuously regenerate the activator thus allowing for a successful ATRP at very mild conditions and in the presence of a low amount of catalyst.…”

Section: Introductionmentioning

confidence: 99%

Oxygen‐enhanced superoxido copper‐catalyzed ATRP accelerated by light

Casa,

Parkatzidis,

Truong

et al. 2023

Journal of Polymer Science

View full text Add to dashboard Cite

Oxygen‐enhanced atom transfer radical polymerization (ATRP) via the formation of a superoxido copper complex, has recently emerged as a powerful tool for the synthesis of well‐defined polymers. However, relatively long reaction times (>8 h) were required to reach high monomer conversions. Herein, we explore the influence of light in this new polymerization procedure. Under UV irradiation, a significant enhancement over the polymerization rate was observed resulting in near‐quantitative monomer consumption (>90%) within 2 h and narrow molar mass distributions (Đ = 1.07). The rate acceleration was attributed to the fast reduction of the superoxido copper complex to Cu(I)Br under UV irradiation, as confirmed via detailed UV–Vis kinetic experiments. In addition, the induction period was completely eliminated, which is in stark contrast to conventional photo‐ATRP (utilizing Cu(II)Br), thus further highlighting the superiority of the presented system. The synergy of the superoxido complex and UV irradiation enabled the synthesis of low‐dispersity homopolymers with molecular weights ranging from 6000 to 300,000. The high end‐group fidelity of the system was further demonstrated via successful in‐situ chain‐extensions.

show abstract

“…18 To probe the fundamental mechanism of CRP, computational chemistry is very powerful. Recently, the Coote group designed and evaluated a series of novel ATRP ligands based on density functional theory (DFT) 19,20 ; investigated the mechanism of reversible additionfragmentation chain transfer (RAFT) reagent via low-energy electron attachment 21 ; and computationally designed the pH-switchable control agent for nitroxide-mediated radical polymerization (NMP). 22 In addition, D'Hooge and Sabbe gave a detailed review of the relationship between quantum chemical calculations (QCC) and kinetic modeling.…”

Section: Introductionmentioning

confidence: 99%

Identifying the essential roles of light and sonication in dual‐stimuli regulated bulk atom transfer radical polymerization by multiscale simulation

et al. 2023

View full text Add to dashboard Cite

More and more attention has been paid to the important roles of external fields in controlled radical polymerization (CRP). However, their essential roles have not been studied thoroughly yet, which hinders the in‐depth understanding of the mechanism and kinetics. Herein, a strategy combining quantum chemical calculations (QCC) and kinetic modeling was adopted to identify the essential roles of light and ultrasonication in the dual‐stimuli regulated bulk atom transfer radical polymerization (ATRP). At the molecular level, the impact of light on Cu‐catalyzed ATRP was investigated. The CuIIBr/Me6TREN has high absorbance at an experimental wavelength of 365 nm (main excitation S0 → D7 accounts for 84.93%). Electron transfer reactions involving Me6TREN are more favorable paths for photochemical reactions, and the mechanism of the copper activation/deactivation pathway is inner sphere electron transfer. At the micro‐scale, a kinetic model based on the method of moment was established with a “series” encounter pair model to consider the influence of ultrasound on diffusional limitation. Simulation results show that the changes of the reaction rate coefficients ka, kda, and kt at high conversion reflect the degree of diffusional limitation by ultrasound. The multiscale modeling strategy applied in this study identifies the essential roles of photo and ultrasonication in dual‐stimuli regulated model systems, which can be extended to other external‐field regulated CRP to improve the mechanistic understanding.

show abstract

Computational design of next generation atom transfer radical polymerization ligands

Abstract: Benchmarked density functional theory is used to design and evaluate a series of novel atom transfer radical polymerization (ATRP) catalysts with a view to identifying those which best promote a...

Cited by 7 publications

References 28 publications

Atom Transfer Radical Polymerization: A Mechanistic Perspective

Atom Transfer Radical Polymerization: A Mechanistic Perspective

Oxygen‐enhanced superoxido copper‐catalyzed ATRP accelerated by light

Identifying the essential roles of light and sonication in dual‐stimuli regulated bulk atom transfer radical polymerization by multiscale simulation

Contact Info

Product

Resources

About