Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

Katherine J. Stawiasz; Chloe I. Wendell; Benjamin A. Suslick; Jeffrey S. Moore

doi:10.1021/acsmacrolett.2c00248

Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

Katherine J. Stawiasz, Chloe I. Wendell, Benjamin A. Suslick, Jeffrey S. Moore

Research output: Contribution to journal › Article › peer-review

Abstract

Herein, we report the development of a photoredox-initiated frontal ring-opening metathesis polymerization (FROMP) chemical system. We found that a ruthenium-based, bis-N-heterocyclic carbene metathesis precatalyst was activated with 9-mesityl-10-phenylacridindium tetrafluoroborate, copper(II) triflate, and a 455 nm light source. This chemistry was used to initiate the FROMP of dicyclopentadiene; once initiated, the heat released from the polymerization sustained a well-controlled reaction front. Variation in copper or metathesis precatalyst loading yielded front speeds ranging from 0.15 to 0.43 mm s^-1 and front temperatures ranging from 140 to 205 °C. While the glass transition temperatures of the resultant polymers are lower than those derived with Grubbs’ second-generation catalyst, this chemical system provides extended pot life.

Original language	English (US)
Pages (from-to)	780-784
Number of pages	5
Journal	ACS Macro Letters
Volume	11
Issue number	6
Early online date	May 27 2022
DOIs	https://doi.org/10.1021/acsmacrolett.2c00248
State	Published - Jun 21 2022

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Online availability

10.1021/acsmacrolett.2c00248

Library availability

Discover UIUC Full Text

Cite this

@article{4f4cc8654091424fa029f7a343e1f32f,

title = "Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization",

abstract = "Herein, we report the development of a photoredox-initiated frontal ring-opening metathesis polymerization (FROMP) chemical system. We found that a ruthenium-based, bis-N-heterocyclic carbene metathesis precatalyst was activated with 9-mesityl-10-phenylacridindium tetrafluoroborate, copper(II) triflate, and a 455 nm light source. This chemistry was used to initiate the FROMP of dicyclopentadiene; once initiated, the heat released from the polymerization sustained a well-controlled reaction front. Variation in copper or metathesis precatalyst loading yielded front speeds ranging from 0.15 to 0.43 mm s-1 and front temperatures ranging from 140 to 205 °C. While the glass transition temperatures of the resultant polymers are lower than those derived with Grubbs{\textquoteright} second-generation catalyst, this chemical system provides extended pot life.",

author = "Stawiasz, {Katherine J.} and Wendell, {Chloe I.} and Suslick, {Benjamin A.} and Moore, {Jeffrey S.}",

note = "This work was primarily funded by NSF CMMI 19-33932. Demeta S.A.S. is thanked for their generous donation of D899 precatalyst, as well as helpful guidance. The authors would like to extend particular thanks to Nafisa Ibrahim of the Joaquin Rodriguez-Lopez group at the University of Illinois at Urbana─Champaign for her help in collecting cyclic voltammograms and discussion thereof. K.J.S. thanks the Department of Defense for an NDSEG fellowship.",

year = "2022",

month = jun,

day = "21",

doi = "10.1021/acsmacrolett.2c00248",

language = "English (US)",

volume = "11",

pages = "780--784",

journal = "ACS Macro Letters",

issn = "2161-1653",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

AU - Stawiasz, Katherine J.

AU - Wendell, Chloe I.

AU - Suslick, Benjamin A.

AU - Moore, Jeffrey S.

N1 - This work was primarily funded by NSF CMMI 19-33932. Demeta S.A.S. is thanked for their generous donation of D899 precatalyst, as well as helpful guidance. The authors would like to extend particular thanks to Nafisa Ibrahim of the Joaquin Rodriguez-Lopez group at the University of Illinois at Urbana─Champaign for her help in collecting cyclic voltammograms and discussion thereof. K.J.S. thanks the Department of Defense for an NDSEG fellowship.

PY - 2022/6/21

Y1 - 2022/6/21

N2 - Herein, we report the development of a photoredox-initiated frontal ring-opening metathesis polymerization (FROMP) chemical system. We found that a ruthenium-based, bis-N-heterocyclic carbene metathesis precatalyst was activated with 9-mesityl-10-phenylacridindium tetrafluoroborate, copper(II) triflate, and a 455 nm light source. This chemistry was used to initiate the FROMP of dicyclopentadiene; once initiated, the heat released from the polymerization sustained a well-controlled reaction front. Variation in copper or metathesis precatalyst loading yielded front speeds ranging from 0.15 to 0.43 mm s-1 and front temperatures ranging from 140 to 205 °C. While the glass transition temperatures of the resultant polymers are lower than those derived with Grubbs’ second-generation catalyst, this chemical system provides extended pot life.

AB - Herein, we report the development of a photoredox-initiated frontal ring-opening metathesis polymerization (FROMP) chemical system. We found that a ruthenium-based, bis-N-heterocyclic carbene metathesis precatalyst was activated with 9-mesityl-10-phenylacridindium tetrafluoroborate, copper(II) triflate, and a 455 nm light source. This chemistry was used to initiate the FROMP of dicyclopentadiene; once initiated, the heat released from the polymerization sustained a well-controlled reaction front. Variation in copper or metathesis precatalyst loading yielded front speeds ranging from 0.15 to 0.43 mm s-1 and front temperatures ranging from 140 to 205 °C. While the glass transition temperatures of the resultant polymers are lower than those derived with Grubbs’ second-generation catalyst, this chemical system provides extended pot life.

UR - http://www.scopus.com/inward/record.url?scp=85131752413&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85131752413&partnerID=8YFLogxK

U2 - 10.1021/acsmacrolett.2c00248

DO - 10.1021/acsmacrolett.2c00248

M3 - Article

C2 - 35638608

AN - SCOPUS:85131752413

SN - 2161-1653

VL - 11

SP - 780

EP - 784

JO - ACS Macro Letters

JF - ACS Macro Letters

IS - 6

ER -

Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization

Abstract

ASJC Scopus subject areas

Online availability

Library availability

Related links

Fingerprint

Cite this