Importance of dynamic hydrogen bonds and reorientation barriers in proton transport

Nagamani, Chikkannagari; Viswanathan, Usha; Versek, Craig; Tuominen, Mark; Auerbach, Scott M.; Thayumanavan, S.

doi:10.1039/c1cc11207d

Cited by 27 publications

(32 citation statements)

References 35 publications

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“…Hence, they lack the contiguous network of hydrogen bonds required for truly facile water-free PT. As noted by Nagamani et al, the presence of a hydrogen bond network is vital to fast and robust PT [38]. Another advantage of a functionalized surface over polymers is the reduced flexibility of the surface relative to a polymer; flexibility in the polymer chain disrupts hydrogen bonds and decreases the PT rate.…”

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confidence: 99%

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Facile Anhydrous Proton Transport on Hydroxyl Functionalized Graphane

et al. 2017

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confidence: 99%

“…Proton conduction on OH functionalized polymers [5,38], ionic crystals [39], and doped amorphous carbons [40] has been demonstrated, but none of these materials have optimal placement of hydrogen bonding groups. Hence, they lack the contiguous network of hydrogen bonds required for truly facile water-free PT.…”

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confidence: 99%

Facile Anhydrous Proton Transport on Hydroxyl Functionalized Graphane

et al. 2017

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“…The Boc protecting groups were deprotected following a reported procedure 13. The appropriate Boc‐protected biaryl polymer was taken in 5 mL DCM at RT under argon and 5 mL TFA was added to it.…”

Section: Methodsmentioning

confidence: 99%

“…It has also been shown, with the help of theoretical modeling, that the pentamers of polystyrene (tri OH) (Fig. 1) can form extended intrachain hydrogen bond network 13. Both intrachain and interchain proton transfer events are important for long range PT.…”

Section: Introductionmentioning

confidence: 99%

“…In the case of N ‐heterocyclic polymers, the reorientation step in Grotthuss proton transport (PT) is well recognized to be energetically demanding, thereby adversely affecting the overall PT 10–12. We have recently introduced a new class of functional groups, phenols, for anhydrous PT and have shown that polymers based on phenols allow for facile reorientational dynamics 13. It has also been shown, with the help of theoretical modeling, that the pentamers of polystyrene (tri OH) (Fig.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and characterization of phenol‐based biaryl proton conducting polymers

Nagamani

Guo

Thayumanavan

2011

J. Polym. Sci. A Polym. Chem.

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Biaryl hydroxy polymers with orthogonal disposition of proton transporting OH moieties have been synthesized via conventional free radical polymerization. The polymers are characterized for their thermal stability and proton conductivity, and the results are compared with the corresponding styrenic hydroxy polymers. The orthogonal disposition of OH moieties in biaryl polymers does result in lower Ea for proton transport. However, the lower Ea values in biaryl polymers did not translate into a net increase in proton conductivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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Bifunctional Polymer Architectures for Cooperative Catalysis: Tunable Acid–Base Polymers for Aldol Condensation

et al. 2016

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Cooperative catalysts combining weak acids and basic amines have been utilized to effectively catalyze aldol and related coupling reactions under mild conditions. Most cooperative chemical catalysts for the aldol reaction have been based on silica‐supported amines. In this work, an alternate approach is demonstrated whereby cooperative amine/acid interactions are tailored through the implementation of polymeric supports. By using linear poly(styrene) supports, this work demonstrates that the design and spacing of monomer units plays an essential role in the cooperativity of the acid–base sites in the aldol condensation. The monomer sequence of each polymer catalyst dramatically affects the catalytic activity, with a random copolymer displaying optimal cooperativity between the acid and base, and block copolymers drastically reducing catalyst activity. Trends established in the silica‐supported systems, such as use of stronger acid monomers demonstrating reduced activity, are verified and extended to these polymer‐supported systems. Overall, this first generation polymer‐supported system is not as efficient as the optimal silica‐supported catalysts developed over the last decade, with the polymers studied here being poorly soluble, leading to inefficient use of the amine sites.

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Importance of dynamic hydrogen bonds and reorientation barriers in proton transport

Abstract: The dynamic nature of hydrogen bonds in phenolic polymers, where the hydrogen bond donor/acceptor reorientation can occur in a single site, presents lower barriers for proton transport.

Cited by 27 publications

References 35 publications

Facile Anhydrous Proton Transport on Hydroxyl Functionalized Graphane

Facile Anhydrous Proton Transport on Hydroxyl Functionalized Graphane

Synthesis and characterization of phenol‐based biaryl proton conducting polymers

Bifunctional Polymer Architectures for Cooperative Catalysis: Tunable Acid–Base Polymers for Aldol Condensation

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