Photo- and thermo-chromism of a ruthenium(II) complex and viologen-containing polymer film

Suzuki, Masahiro; Kimura, Mutsumi; Shirai, Hirofusa

doi:10.1039/a705107g

Cited by 20 publications

(6 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The rate of thermal reverse electron transfer is usually very high, which precludes the use of these systems for solar energy conversion. However, it has been shown that stabilization of viologen radical cations can be achieved by their incorporation to solid matrices, such as zeolites, , polymers, , Langmuir–Blodgett monolayers, crystal frameworks, − and hybrid structures. − …”

Section: Introductionmentioning

confidence: 99%

Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals

et al. 2017

View full text Add to dashboard Cite

Methyl viologen hexafluorophosphate (MV·2PF) and dodecamethylbambus[6]uril (BU6) form crystals in which the layers of viologen dications alternate with those of a 1:2 supramolecular complex of BU6 and PF. This arrangement allows for a one-electron reduction of MV ions upon UV irradiation to form MV radical cations within the crystal structure with half-lives of several hours in air. The mechanism of this photoinduced electron transfer in the solid state and the origin of the long-lived charge-separated state were studied by steady-state and transient spectroscopies, cyclic voltammetry, and electron paramagnetic resonance spectroscopy. Our experiments are supported by quantum-chemical calculations showing that BU6 acts as a reductant. In addition, analogous photochemical behavior is also demonstrated on other MV/BU6 crystals containing either BF or Br counterions.

show abstract

Section: Introductionmentioning

confidence: 99%

Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals

et al. 2017

View full text Add to dashboard Cite

show abstract

“…The incorporation of redox-active functional groups, such as ferrocene, metal complexes, nitroxides, or catechols, etc., in the PILs chain forms “redox-active PILs”, an emerging family of PILs of high interest for energy applications. As selected examples, some of them were explored as PILs-modified electrodes in molecular electronics, (bio)analytical sensors, electrochemical actuators, and energy transduction materials. − These redox-active PILs were obtained either via postmodification of neutral polymer precursors − or by direct polymerization of the functional monomer, protected or not, depending on the polymerization technique that was used for their production. − For instance, when radical polymerization of redox-active IL monomer is considered, the scavenging ability of catechol or nitroxide groups may cause inhibition and/or impede the radical polymerization and/or lead to side reactions (such as branching). − The precision synthesis of PILs-bearing catechols by CRP therefore remains difficult. In order to avoid these side reactions, catechol-protecting group chemistry has been performed.…”

Section: Introductionmentioning

confidence: 99%

Surface- and Redox-Active Multifunctional Polyphenol-Derived Poly(ionic liquid)s: Controlled Synthesis and Characterization

et al. 2016

View full text Add to dashboard Cite

Combining 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/pyrogallolderived PILs in aqueous medium demonstrated the characteristic catechol to o-quinone transformations, whereas, quasireversible 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.

show abstract

“…However, viologen dications are generally soluble in water, and hence it is difficult to retain them on substrates for possible applications in aqueous solutions. To circumvent this problem, insoluble polymers with viologen moieties have been synthesized. ,− Other studies have been carried out with viologens incorporated into anionic polyelectrolyte films and in zeolites matrixes. , Our group and others have carried out surface modification of polymeric substrates via graft copolymerization to impart new and specific functionalities to the polymer surface, − and this technique can also be employed for the immobilization of viologens.…”

Section: Introductionmentioning

confidence: 99%

Surface Functionalization of Glass and Polymeric Substrates via Graft Copolymerization of Viologen in an Aqueous Medium

et al. 2002

View full text Add to dashboard Cite

Surface functionalization of low-density polyethylene (LDPE), silanized glass, and free-standing polyaniline (PANI) films via UV-induced graft copolymerization with 1,1‘-bis(4-vinyl-benzyl)-4,4‘-bipyridinium dichloride (VBV) was carried out. The vinyl group containing viologen was synthesized by the double Anderson reaction using 4,4‘-bipyridine and vinyl benzyl chloride and characterized by elemental analysis, FTIR spectrum, and X-ray photoelectron spectroscopy. The graft copolymerization of VBV was carried out by placing the plasma-pretreated substrate in contact with an aqueous solution of VBV under UV irradiation. The effects of the plasma-pretreatment time of the substrate, UV-induced graft copolymerization time, and monomer concentration on the VBV-graft copolymer concentration were investigated. The responses of the VBV-graft-copolymerized LDPE films and silanized glass slides to photoirradiation were monitored. In both cases, intensely blue viologen radical cations were formed after 10 min of UV irradiation in a vacuum and bleaching occurred when the substrate was exposed to air upon termination of the irradiation. VBV-graft-copolymerized PANI films with good conductivity can be prepared, and these films may have possible applications as active templates in biosensors where the viologen groups may serve as electron transfer mediators from the electrode surface to the active site of biomaterials. This method of surface functionalization of viologen moieties offers a number of advantages over a previously developed technique.

show abstract

Photo- and thermo-chromism of a ruthenium(II) complex and viologen-containing polymer film

Cited by 20 publications

References 16 publications

Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals

Bambusuril as a One-Electron Donor for Photoinduced Electron Transfer to Methyl Viologen in Mixed Crystals

Surface- and Redox-Active Multifunctional Polyphenol-Derived Poly(ionic liquid)s: Controlled Synthesis and Characterization

Surface Functionalization of Glass and Polymeric Substrates via Graft Copolymerization of Viologen in an Aqueous Medium

Contact Info

Product

Resources

About