Poly[n]catenanes: Synthesis of molecular interlocked chains

doi:10.1126/science.aap7675

Title: Poly[ n]catenanes: Synthesis of molecular interlocked chains

Abstract

As the macromolecular version of mechanically interlocked molecules, mechanically interlocked polymers are promising candidates for the creation of sophisticated molecular machines and smart soft materials. Poly[ n]catenanes, where the molecular chains consist solely of interlocked macrocycles, contain one of the highest concentrations of topological bonds. We report, herein, a synthetic approach toward this distinctive polymer architecture in high yield (similar to 75%) via efficient ring closing of rationally designed metallosupramolecular polymers. Light-scattering, mass spectrometric, and nuclear magnetic resonance characterization of fractionated samples support assignment of the high-molar mass product (number-average molar mass similar to 21.4 kilograms per mole) to a mixture of linear poly[7-26]catenanes, branched poly[13-130]catenanes, and cyclic poly[4-7]catenanes. As a result, increased hydrodynamic radius (in solution) and glass transition temperature (in bulk materials) were observed upon metallation with Zn ²⁺.

Authors:

^[1];

^[2];

^[3];

^[3]; de Pablo, Juan J. ^[4];

^[3];

^[5]

Univ. of Chicago, Chicago, IL (United States); Case Western Reserve Univ., Cleveland, OH (United States)
Univ. of Chicago, Chicago, IL (United States)
Case Western Reserve Univ., Cleveland, OH (United States)
Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, Chicago, IL (United States); Case Western Reserve Univ., Cleveland, OH (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Publication Date:: 2017-12-15

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: National Science Foundation (NSF); USDOE

OSTI Identifier:: 1425221

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Science

Additional Journal Information:: Journal Volume: 358; Journal Issue: 6369; Journal ID: ISSN 0036-8075

Publisher:: AAAS

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Wu, Qiong, Rauscher, Phillip M., Lang, Xiaolong, Wojtecki, Rudy J., de Pablo, Juan J., Hore, Michael J. A., and Rowan, Stuart J. Poly[n]catenanes: Synthesis of molecular interlocked chains.  United States: N. p., 2017. 
        Web.  doi:10.1126/science.aap7675.

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                    Wu, Qiong, Rauscher, Phillip M., Lang, Xiaolong, Wojtecki, Rudy J., de Pablo, Juan J., Hore, Michael J. A., & Rowan, Stuart J. Poly[n]catenanes: Synthesis of molecular interlocked chains.  United States.  doi:10.1126/science.aap7675.

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                    Wu, Qiong, Rauscher, Phillip M., Lang, Xiaolong, Wojtecki, Rudy J., de Pablo, Juan J., Hore, Michael J. A., and Rowan, Stuart J. Fri .  
        "Poly[n]catenanes: Synthesis of molecular interlocked chains".  United States.  doi:10.1126/science.aap7675.  https://www.osti.gov/servlets/purl/1425221.

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@article{osti_1425221,

  title        = {Poly[n]catenanes: Synthesis of molecular interlocked chains},

  author       = {Wu, Qiong and Rauscher, Phillip M. and Lang, Xiaolong and Wojtecki, Rudy J. and de Pablo, Juan J. and Hore, Michael J. A. and Rowan, Stuart J.},

  abstractNote = {As the macromolecular version of mechanically interlocked molecules, mechanically interlocked polymers are promising candidates for the creation of sophisticated molecular machines and smart soft materials. Poly[n]catenanes, where the molecular chains consist solely of interlocked macrocycles, contain one of the highest concentrations of topological bonds. We report, herein, a synthetic approach toward this distinctive polymer architecture in high yield (similar to 75%) via efficient ring closing of rationally designed metallosupramolecular polymers. Light-scattering, mass spectrometric, and nuclear magnetic resonance characterization of fractionated samples support assignment of the high-molar mass product (number-average molar mass similar to 21.4 kilograms per mole) to a mixture of linear poly[7-26]catenanes, branched poly[13-130]catenanes, and cyclic poly[4-7]catenanes. As a result, increased hydrodynamic radius (in solution) and glass transition temperature (in bulk materials) were observed upon metallation with Zn2+.},

  doi          = {10.1126/science.aap7675},

  journal      = {Science},

  number       = 6369,

  volume       = 358,

  place        = {United States},

  year         = {2017},

  month        = {12}

}

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DOI: 10.1126/science.aap7675

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Works referenced in this record:

Optically healable supramolecular polymers
journal, April 2011

Burnworth, Mark; Tang, Liming; Kumpfer, Justin R.
Nature, Vol. 472, Issue 7343, p. 334-337
DOI: 10.1038/nature09963

An "Endless" Route to Cyclic Polymers
journal, September 2002

Bielawski, Christopher W.; Benitez, Diego; Grubbs, Robert H.
Science, Vol. 297, Issue 5589, p. 2041-2044
DOI: 10.1126/science.1075401

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Title: Poly[ n]catenanes: Synthesis of molecular interlocked chains

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Citation Formats

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An "Endless" Route to Cyclic Polymers journal, September 2002

Optically healable supramolecular polymers
journal, April 2011

An "Endless" Route to Cyclic Polymers
journal, September 2002