Engineering Surfaces through Sequential Stop‐Flow Photopatterning

Pester, Christian W.; Narupai, Benjaporn; Mattson, Kaila M.; Bothman, David P.; Klinger, Daniel; Lee, Kenneth W.; Discekici, Emre H.; Hawker, Craig J.

doi:10.1002/adma.201602900

Cited by 80 publications

(82 citation statements)

References 50 publications

(86 reference statements)

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“…), a reducing organic photoredox catalyst—10‐phenylphenothiazine (PTH)—has been developed for the light‐mediated removal of halogen chain‐ends from styrenic, acrylic and methacrylic polymers . This quantitative method is readily applicable to thin films, enabling the facile preparation of hierarchical patterned polymer brush films …”

Section: Discussionmentioning

confidence: 99%

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Established and emerging strategies for polymer chain‐end modification

Lunn

Discekici

Alaniz

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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The development of "controlled" and "living" polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chainend functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods.

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Section: Discussionmentioning

confidence: 99%

“… Transferal of small molecule organic chemistry for the chain‐end modification of polymers. Photochemical dehalogenation of polymers, and polymer brush surfaces using PTH. Typical reaction conditions: 5 mol% PTH, HCOOH (5 equiv.)…”

Section: Discussionmentioning

confidence: 99%

Established and emerging strategies for polymer chain‐end modification

Lunn

Discekici

Alaniz

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…In contrast to the thermal reactions described by Hayashi and Studer, we have found that the synthesis of n‐type CPs requires photochemical conditions. Photopolymerizations offer the opportunity for spatiotemporal control and selective catalyst activation by different wavelengths of light . For non‐conjugated polymers, researchers have developed a range of photocontrolled polymerizations .…”

Section: Introductionmentioning

confidence: 99%

“…conditions.P hotopolymerizations offer the opportunity for spatiotemporal control [16][17][18] and selective catalyst activation by different wavelengths of light. [19][20][21] Forn on-conjugated polymers,r esearchers have developed ar ange of photocontrolled polymerizations.…”

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confidence: 99%

Photocontrolled Synthesis of n‐Type Conjugated Polymers

2020

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Current approaches to synthesize π‐conjugated polymers (CPs) are dominated by thermally driven, transition‐metal‐mediated reactions. Herein we show that electron‐deficient Grignard monomers readily polymerize under visible‐light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain‐growth process; correspondingly, chain extension produces all‐conjugated n‐type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor–acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n‐type CPs without the need for transition‐metal catalysis.

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“…30,31 In particular, surface initiated atom transfer radical polymerization (SI-ATRP) catalyzed by photoactive Ir(III) phosphors can be used to pattern polymer brushes using visible light, 32 and the “living” nature of this process permits hierarchical patterning of block copolymer brush architectures with submicron feature resolution. 26 …”

Section: Introductionmentioning

confidence: 99%

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications

Page¹,

Narupai²,

Pester³

et al. 2017

ACS Cent. Sci.

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A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red–green–blue arrays to yield white emission.

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Engineering Surfaces through Sequential Stop‐Flow Photopatterning

Cited by 80 publications

References 50 publications

Established and emerging strategies for polymer chain‐end modification

Established and emerging strategies for polymer chain‐end modification

Photocontrolled Synthesis of n‐Type Conjugated Polymers

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications

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