Charge separation in the light‐induced electron transfer reaction of amphiphilic copolymers consisting of polyanion and phenanthrene segments

Itoh, Yoshifumi; Morishima, Yotaro; Nozakura, Shun‐ichi

doi:10.1002/pol.1983.130210303

Cited by 8 publications

(1 citation statement)

References 10 publications

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“…In a series of studies on polyelectrolytes functionalized with polycyclic aromatic groups as photoactive centers, we have demonstrated that the macromolecular microenvironments can have critical effects in various ways on photoredox reaction (Morishima et al, 1981(Morishima et al, , 1982a(Morishima et al, , 1982bItoh et al, 1982Itoh et al, , 1983Itoh et al, , 1984a. Recent studies have shown that the local electrostatic potential of the polyelectrolytes plays a decisive role over the fate of the ionic photoproducts (Itoh et al, 1984b;Morishima et al, 1984).…”

Section: Introductionmentioning

confidence: 99%

Syntheses and Photoredox Properties of Polyelectrolytes Functionalized With 5‐deazaflavin

Morishima

Kitani

Kobayashi

et al. 1985

Photochem & Photobiology

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Abstract— Anionic polyelectrolytes functionalized with the 5‐deazaflavin group (dFl) were synthesized. The lifetime of the triplet excited dFl in the polyelectrolytes with a 2‐mol% dFl content (AdFl‐2) was about 10 times longer than that of a low molecular weight analog (AdFl‐M). 2‐Mercaptoethanol (RSH) reduced the triplet dFl with the rate constant of kred= 2.01 × 108M−1 s−1 for AdFl‐M and kred= 4.4 × 107M−1 s−1 for AdFl‐2. A zwitterionic viologen (SPV) oxidized the triplet dFl with the rate constant of kred= 3.69 × 109M−1 s−1 for AdFl‐M and kox= 7.4 × 108 M−1 s−1 for AdFl‐2. The smaller rate constants for the polymer system were discussed in terms of the hindering effect of the macromolecular microenvironment. The back electron transfer was shown to be drastically slowed in the AdFl‐2‐SPV system as a result of the intensive electrostatic effect of the polyelectrolytes. The buildup of the viologen radicals was studied under the steady‐state illumination of the three component systems including viologen and RSH. The dFl group was demonstrated to serve as a very efficient photosensitizer in the oxidative cycle in case back electron transfer was retarded. This is the case of the AdFl‐2‐SPV system which gave the quantum yield of about 0.4 for the SPV− buildup. By comparison, the AdFl‐2‐MV2+ system resulted in a much slower buildup of MV +radicals.

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Section: Introductionmentioning

confidence: 99%

Syntheses and Photoredox Properties of Polyelectrolytes Functionalized With 5‐deazaflavin

Morishima

Kitani

Kobayashi

et al. 1985

Photochem & Photobiology

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Diquaternary Salts of 4,4′‐Bipyridine as Electron Relays for the Photoreduction of Water

Summers

1991

Journal of Heterocyclic Chem

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Efficiency of polymer sensitizer in photosensitized reaction of tris(bipyridine)ruthenium(II) complex‐containing polymer

Sumi

Furue

Nozakura

1985

J. Polym. Sci. Polym. Chem. Ed.

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Photochemical properties of Ru(bpy)2(poly‐4‐methyl‐4′‐vinyl‐2,2′‐bipyridine)Cl2 (2) were studied and compared with that of Ru(bpy)3Cl2. Continuous irradiation of a solution, which contains polymer 2 as a photosensitizer, methylviologen (MV2+) or 4,4′‐bipyridinium‐1,1′‐bis(trimethylenesulfonate) (SPV) as an electron acceptor and triethanolamine (TEOA) as a sacrificial donor, resulted in the formation of viologen radical ion (MV+ or SPV−). The rate of formation of MV+ or SPV− for the polymer 2 system was smaller than that for the Ru(bpy)3 Cl2 systems. The reason for this fact was kinetically analyzed by quenching experiments of excited Ru(II) complexes by MV2+ or SPV, the photosensitized reactions of the TEOA–Ru(II) complex–MV2+ or ‐SPV systems, and the dye laser photolysis of the Ru(II) complex–MV2+ or ‐SPV systems.

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Charge separation in the light‐induced electron transfer reaction of amphiphilic copolymers consisting of polyanion and phenanthrene segments

Cited by 8 publications

References 10 publications

Syntheses and Photoredox Properties of Polyelectrolytes Functionalized With 5‐deazaflavin

Syntheses and Photoredox Properties of Polyelectrolytes Functionalized With 5‐deazaflavin

Diquaternary Salts of 4,4′‐Bipyridine as Electron Relays for the Photoreduction of Water

Efficiency of polymer sensitizer in photosensitized reaction of tris(bipyridine)ruthenium(II) complex‐containing polymer

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