Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films

Trinh, Thi Kim Hoang; Schrodj, Gautier; Rigolet, Séverinne; Pinaud, Julien; Lacroix‐Desmazes, Patrick; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

doi:10.1039/c9ra05831a

Cited by 20 publications

(19 citation statements)

References 67 publications

(116 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Another example reported in 2019 by Chemtob and coworkers used Noel's catalyst (53) as the precatalyst, which was generated in situ from a labile dimeric Ru II complex ([RuCl 2 (p-cymene)] 2 ) and an NHC generator. 506 It was found that the formation of the active NHC by photodeprotonation of 1,3-bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 − ) was more efficient through a sensitized reaction with addition of isopropylthioxanthone (ITX) under 365 nm light than the direct photolysis utilizing 254 nm light. Increasing the amount of ITX led to higher conversion of NB (78% with 2.5 equiv of ITX vs 94% with 5 equiv of ITX) within 1 min because more NHC was generated to form 53.…”

Section: Photochemical Controlmentioning

confidence: 99%

Advances in Polymerizations Modulated by External Stimuli

et al. 2020

View full text Add to dashboard Cite

Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, and applications. This is often approached through the development of dynamic catalyst (or initiator) systems that use external stimuli to elicit discrete, site-specific transformations that impact the polymerization. Herein we highlight developments in polymerizations that are modulated by external stimuli, with particular focus on those systems that enable notable changes in kinetics, monomer selectivity, polymer architecture, or tacticity. Examples of external stimuli include chemical oxidants or reductants, light, applied voltage, and mechanical force.

show abstract

Section: Photochemical Controlmentioning

confidence: 99%

Advances in Polymerizations Modulated by External Stimuli

et al. 2020

View full text Add to dashboard Cite

show abstract

“…27 Owing to ROMP, numerous polymers and polymeric materials like biomedical functional materials, ion exchange membranes, photoresist and photoinitiated polymers have been synthesized easily. [28][29][30][31][32][33][34] With the aid of frontal polymerization technique, ROMP was also applied for rapid manufacture of high-performance cross-linked polymers and materials. 35 If diols were converted to cyclic olefins moiety-containing monomers, they can be used to generate polymers via ROMP, which benefit to reduce the energy and expand their applications.…”

Section: Introductionmentioning

confidence: 99%

Rapid synthesis of diol homolog-based thermosets with tunable propertiesviaring-opening metathesis polymerization

Zhang

Huangfu

et al. 2021

Mater. Adv.

View full text Add to dashboard Cite

show abstract

“…Since the emergence of well-defined transition metal catalysts, olefin metathesis has evolved to become a handy paintbrush for molecular artists in industry and academia. 5 With a plethora of options to form and reshape carbon–carbon double bonds, olefin metathesis is the method of choice for the synthesis of macrocycles 6 and heavy-duty polymeric materials 7 and even for the preparation of simple commodity chemicals from oil waste products and biomass. 8 The flexible framework of ruthenium-based complexes has opened up many research avenues for the development of task-specific catalysts, 9 such as catalysts embedded with asymmetric ligands for enantioselective olefin metathesis reactions, 10 catalysts that specialize in ring-closing metathesis (RCM) of macrocyclic structures, 11 catalysts for Z -selective 12 and stereoretentive 13 olefin metathesis reactions, and fast-initiating catalysts for ring-opening metathesis polymerization (ROMP).…”

Section: Introductionmentioning

confidence: 99%

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

et al. 2020

View full text Add to dashboard Cite

Conspectus The most important means for tuning and improving a catalyst’s properties is the delicate exchange of the ligand shell around the central metal atom. Perhaps for no other organometallic-catalyzed reaction is this statement more valid than for ruthenium-based olefin metathesis. Indeed, even the simple exchange of an oxygen atom for a sulfur atom in a chelated ruthenium benzylidene about a decade ago resulted in the development of extremely stable, photoactive catalysts. This Account presents our perspective on the development of dormant olefin metathesis catalysts that can be activated by external stimuli and, more specifically, the use of light as an attractive inducing agent. The insight gained from a deeper understanding of the properties of cis -dichlororuthenium benzylidenes opened the doorway for the systematic development of new and efficient light-activated olefin metathesis catalysts and catalytic chromatic-orthogonal synthetic schemes. Following this, ways to disrupt the ligand-to-metal bond to accelerate the isomerization process that produced the active precatalyst were actively pursued. Thus, we summarize herein the original thermal activation experiments and how they brought about the discoveries of photoactivation in the sulfur-chelated benzylidene family of catalysts. The specific wavelengths of light that were used to dissociate the sulfur–ruthenium bond allowed us to develop noncommutative catalytic chromatic-orthogonal processes and to combine other photochemical reactions with photoinduced olefin metathesis, including using external light-absorbing molecules as “sunscreens” to achieve novel selectivities. Alteration of the ligand sphere, including modifications of the N-heterocyclic carbene (NHC) ligand and the introduction of cyclic alkyl amino carbene (CAAC) ligands, produced more efficient light-induced activity and special chemical selectivity. The use of electron-rich sulfoxides and, more prominently, phosphites as the agents that induce latency widened the spectrum of light-induced olefin metathesis reactions even further by expanding the colors of light that may now be used to activate the catalysts, which can be used in applications such as stereolithography and 3D printing of tough metathesis-derived polymers.

show abstract

Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films

Abstract: Photoactivated ROMP is harnessed for the single-step formation of cross-linked polymer coatings based on norbornene and dicyclopentadiene.

Cited by 20 publications

References 67 publications

Advances in Polymerizations Modulated by External Stimuli

Advances in Polymerizations Modulated by External Stimuli

Rapid synthesis of diol homolog-based thermosets with tunable propertiesviaring-opening metathesis polymerization

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

Contact Info

Product

Resources

About