Humidity-modulated phase control and nanoscopic transport in supramolecular assemblies

SMC Author

Mark Lingwood

SMC Affiliated Work

1

Status

Faculty

School

School of Science

Department

Chemistry

Document Type

Article

Publication Date

2-20-2014

Publication / Conference / Sponsorship

Journal of Physical Chemistry B

Description/Abstract

Supramolecular assembly allows for enhanced control of bulk material properties through the fine modulation of intermolecular interactions. We present a comprehensive study of a cross-linkable amphiphilic wedge molecule based on a sulfonated trialkoxybenzene with a sodium counterion that forms liquid crystalline (LC) phases with ionic nanochannel structures. This compound exhibits drastic structural changes as a function of relative humidity (RH). Our combined structural, dynamical, and transport studies reveal deep and novel information on the coupling of water and wedge molecule transport to structural motifs, including the significant influence of domain boundaries within the material. Over a range of RH values, we employ 23Na solid-state NMR on the counterions to complement detailed structural studies by grazing-incidence small-angle X-ray scattering. RH-dependent pulsed-field-gradient (PFG) NMR diffusion studies on both water and the wedge amphiphiles show multiple components, corresponding to species diffusing within LC domains as well as in the domain boundaries that compose 10% of the material. The rich transport and dynamical behaviors described here represent an important window into the world of supramolecular soft materials, carrying implications for optimization of these materials in many venues. Cubic phases present at high RH show fast transport of water (2 × 10–10 m2/s), competitive with that observed in benchmark polymeric ion conductors. Understanding the self-assembly of these supramolecular building blocks shows promise for generating cross-linked membranes with fast ion conduction for applications such as next-generation batteries.

Scholarly

yes

DOI

10.1021/jp409266r

Volume

118

Issue

11

First Page

3207

Last Page

3217

Disciplines

Chemistry | Physical Chemistry

Original Citation

Mark Lingwood (Chemistry): “Humidity-modulated phase control and nanoscopic transport in supramolecular assemblies,” with Y. Chen*, M. Goswami, B.E. Kidd, J.J. Hernandez, M. Rosenthal, D.A. Ivanov, J. Perlich, H. Zhang, X. Zhu, M. Möller, L.A. Madsen, in the Journal of Physical Chemistry B 118 (2014) 3207-3217. doi:10.1021/jp409266r.

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