Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

Suk Kyun Ahn; Deanna L. Pickel; W. Michael Kochemba; Jihua Chen; David Uhrig; Juan Pablo Hinestrosa; Jan Michael Carrillo; Ming Shao; Changwoo Do; Jamie M. Messman; W. Michael Brown; Bobby G. Sumpter; S. Michael Kilbey

doi:10.1021/mz4003563

Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

Suk Kyun Ahn
, Deanna L. Pickel
, W. Michael Kochemba
, Jihua Chen
, David Uhrig
, Juan Pablo Hinestrosa
, Jan Michael Carrillo
, Ming Shao
, Changwoo Do
, Jamie M. Messman
, W. Michael Brown
, Bobby G. Sumpter
, S. Michael Kilbey

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

50 Scopus citations

Abstract

We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of π–π interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.

Original language	English
Pages (from-to)	761-765
Number of pages	5
Journal	ACS Macro Letters
Volume	2
Issue number	8
DOIs	https://doi.org/10.1021/mz4003563
State	Published - Aug 20 2013

Funding

This research was conducted at the Center for Nanophase Materials Sciences (CNMS) and the Leadership Computing Facility (OLCF), which are sponsored at Oak Ridge National Laboratory (ORNL) by the Division of Scientific User Facilities, U.S. Department of Energy, managed by UT-Battelle, LLC. S.-K.A. acknowledges fruitful discussions with Prof. B. Boudouris and Prof. J. Mays, Drs. K. Hong, B. Lokitz, R. Kumar, and J. Keum. W.M.K. and S.M.K. acknowledge support from TN-SCORE which is sponsored by NSF EPSCOR (EPS-1004083).

Access to Document

10.1021/mz4003563

Cite this

Ahn, S. K., Pickel, D. L., Kochemba, W. M., Chen, J., Uhrig, D., Hinestrosa, J. P., Carrillo, J. M., Shao, M., Do, C., Messman, J. M., Brown, W. M., Sumpter, B. G., & Kilbey, S. M. (2013). Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation. ACS Macro Letters, 2(8), 761-765. https://doi.org/10.1021/mz4003563

@article{d76c9c24cdb94664ac1a65b56cd156d9,

title = "Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation",

abstract = "We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of π{\textendash}π interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.",

author = "Ahn, \{Suk Kyun\} and Pickel, \{Deanna L.\} and Kochemba, \{W. Michael\} and Jihua Chen and David Uhrig and Hinestrosa, \{Juan Pablo\} and Carrillo, \{Jan Michael\} and Ming Shao and Changwoo Do and Messman, \{Jamie M.\} and Brown, \{W. Michael\} and Sumpter, \{Bobby G.\} and Kilbey, \{S. Michael\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2013 American Chemical Society",

year = "2013",

month = aug,

day = "20",

doi = "10.1021/mz4003563",

language = "English",

volume = "2",

pages = "761--765",

journal = "ACS Macro Letters",

issn = "2161-1653",

publisher = "American Chemical Society",

number = "8",

}

Ahn, SK, Pickel, DL, Kochemba, WM, Chen, J, Uhrig, D, Hinestrosa, JP, Carrillo, JM, Shao, M, Do, C, Messman, JM, Brown, WM, Sumpter, BG & Kilbey, SM 2013, 'Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation', ACS Macro Letters, vol. 2, no. 8, pp. 761-765. https://doi.org/10.1021/mz4003563

TY - JOUR

T1 - Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization

T2 - Macromolecular Architecture Enhanced Aggregation

AU - Ahn, Suk Kyun

AU - Pickel, Deanna L.

AU - Kochemba, W. Michael

AU - Chen, Jihua

AU - Uhrig, David

AU - Hinestrosa, Juan Pablo

AU - Carrillo, Jan Michael

AU - Shao, Ming

AU - Do, Changwoo

AU - Messman, Jamie M.

AU - Brown, W. Michael

AU - Sumpter, Bobby G.

AU - Kilbey, S. Michael

PY - 2013/8/20

Y1 - 2013/8/20

N2 - We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of π–π interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.

AB - We report a facile synthetic strategy based on a grafting through approach to prepare well-defined molecular bottlebrushes composed of regioregular poly(3-hexylthiophene) (rr-P3HT) as the conjugated polymeric side chain. To this end, the exo-norbornenyl-functionalized P3HT macromonomer was synthesized by Kumada catalyst transfer polycondensation (KCTP) followed by postpolymerization modifications, and the resulting conjugated macromonomer was successfully polymerized by ring-opening metathesis polymerization (ROMP) in a controlled manner. The P3HT molecular bottlebrushes display an unprecedented strong physical aggregation upon drying during recovery, as verified by several analyses of the solution and solid states. This remarkably strong aggregation behavior is attributed to a significant enhancement in the number of π–π interactions between grafted P3HT side chains, brought about due to the bottlebrush architecture. This behavior is qualitatively supported by coarse-grained molecular dynamics simulations.

UR - https://www.scopus.com/pages/publications/84883100463

U2 - 10.1021/mz4003563

DO - 10.1021/mz4003563

M3 - Letter

AN - SCOPUS:84883100463

SN - 2161-1653

VL - 2

SP - 761

EP - 765

JO - ACS Macro Letters

JF - ACS Macro Letters

IS - 8

ER -

Poly(3-hexylthiophene) Molecular Bottlebrushes via Ring-Opening Metathesis Polymerization: Macromolecular Architecture Enhanced Aggregation

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this