ma6b01857_si_001.pdf (3.84 MB)
Surface- and Redox-Active Multifunctional Polyphenol-Derived Poly(ionic liquid)s: Controlled Synthesis and Characterization
journal contribution
posted on 2016-09-30, 17:55 authored by Nagaraj Patil, Daniela Cordella, Abdelhafid Aqil, Antoine Debuigne, Shimelis Admassie, Christine Jérôme, Christophe DetrembleurCombining the redox activity and
remarkable adhesion propensity of polyphenols (such as catechol or
pyrogallol) with the numerous tunable properties of poly(ionic liquid)s
(PILs) is an attractive route to design inventive multifunctional
macromolecular platforms. In this contribution, we describe the first
synthesis of a novel family of structurally well-defined PILs functionalized
with catechol/pyrogallol/phenol pendants by organometallic-mediated
radical polymerization (OMRP) using an alkyl–cobalt(III) complex
as initiator and mediating agent. The living character of the chains
is also exploited to produce di- and triblock PILs, and the facile
counteranion exchange reactions afforded a library of PILs-bearing
free phenol/catechol/pyrogallol moieties. Electrochemical investigations
of catechol/pyrogallol-derived PILs in aqueous medium demonstrated
the characteristic catechol to o-quinone transformations,
whereas, quasi-reversible doping/undoping with supporting electrolyte
cations (Li+/tetrabutylammonium+) has
been observed in organic media, suggesting a bright future for this
new family of redox-active PILs as cathode material for secondary
energy storage devices. Also, pendant catechol/pyrogallol groups mediated
sustained anchoring onto the gold surface conferred PILs properties
to the interface. As a proof-of-concept, both the adsorption and inhibition
of proteins on polymer modified surfaces have been demonstrated in
real time using the quartz crystal microbalance with dissipation technique.
The exquisite physicochemical tunability of these innovative surface-
and redox-active PILs makes them excellent candidates for a broad
range of potential applications, including “smart surfaces”
and electrochemical energy storage devices.