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Synthesis of Isocyanate-Based Brush Block Copolymers and Their Rapid Self-Assembly to Infrared-Reflecting Photonic Crystals

Miyake, Garret M. and Weitekamp, Raymond A. and Piunova, Victoria A. and Grubbs, Robert H. (2012) Synthesis of Isocyanate-Based Brush Block Copolymers and Their Rapid Self-Assembly to Infrared-Reflecting Photonic Crystals. Journal of the American Chemical Society, 134 (34). pp. 14249-14254. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20120907-091822265

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Abstract

The synthesis of rigid-rod, helical isocyanate-based macromonomers was achieved through the polymerization of hexyl isocyanate and 4-phenylbutyl isocyanate, initiated by an exo-norbornene functionalized half-titanocene complex. Sequential ruthenium-mediated ring-opening metathesis polymerization of these macromonomers readily afforded well-defined brush block copolymers, with precisely tunable molecular weights ranging from high (1512 kDa) to ultrahigh (7119 kDa), while maintaining narrow molecular weight distributions (PDI = 1.08–1.39). The self-assembly of these brush block copolymers to solid thin-films and their photonic properties were investigated. Due to the rigid architecture of these novel polymeric materials, they rapidly self-assemble through simple controlled evaporation to photonic crystal materials that reflect light from the ultra-violet, through the visible, to the near-infrared. The wavelength of reflectance is linearly related to the brush block copolymer molecular weight, allowing for predictable tuning of the band gap through synthetic control of the polymer molecular weight. A combination of scanning electron microscopy and optical modeling was employed to explain the origin of reflectivity.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja306430kDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja306430kPublisherArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 2012 American Chemical Society. Received: July 2, 2012. Published: August 14, 2012. This work was supported by the NSF (CHE-1048404). R.A.W. thanks the Resnick Institute for a graduate fellowship.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NSFCHE-1048404
Resnick Institute Graduate FellowshipUNSPECIFIED
Record Number:CaltechAUTHORS:20120907-091822265
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20120907-091822265
Official Citation:Synthesis of Isocyanate-Based Brush Block Copolymers and Their Rapid Self-Assembly to Infrared-Reflecting Photonic Crystals Garret M. Miyake, Raymond A. Weitekamp, Victoria A. Piunova, and Robert H. Grubbs Journal of the American Chemical Society2012134 (34), 14249-14254
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33924
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Sep 2012 16:32
Last Modified:08 Dec 2016 00:20

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