The Interaction of the Tris(2,2′-bipyridine)ruthenium(II) Ion with Poly(<i>p</i>-styrenesulfonate)

Kurimura, Yoshimi; Yokota, Hiroshi; Shigehara, Kiyotaka; Tsuchida, Eishun

doi:10.1246/bcsj.55.55

Cited by 24 publications

(16 citation statements)

References 12 publications

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“…40 No evidence for complex formation between the polyviologens and the ruthenium complexes could be observed, and the rates of both the forward and backward reactions taking place in the photochemical systems were not found to exceed the diffusioncontrolled limit as has been observed previously for reactions of other polyvi~logens'~~'~ and other polyelectrolytes where hydrophobic interactions are important. and BSV-S.~ They may also be similar to the strong hydrophobic interactions observed between the 2,2'-bipyridine or 1,lO-phenanthroline ligands and the phenyl group of poly(styrenesu1fonate).…”

Section: Systems Containing R~( B P Y )~ ' Asmentioning

confidence: 49%

Charge separation in photoinitiated electron-transfer systems with polyviologen polyelectrolytes as quenchers

Gershuni¹,

Rabani²

1985

J. Phys. Chem.

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1937rings, respectively. This suggestion is consistent with the observed Si/Al ratio for ferrierite. The present calculations further indicate that diagonal pairing is favored relative to the meta or ortho pairings in accordance with electrostatic principles and the aluminum avoidance rule.2. As observed in our previous work on mordenite and ZSM-5, the analysis of the formal atomic charges distributions in the clusters indicates the highly covalent nature of aluminosilicate frameworks. The spreading of the negative charge; associated with the presence of Al, indicates that the anionic framework behaves as weak but a soft base.The results presented in this paper complement our earlier findings16J7 and confirm the general principles which have been delineated to describe the behavior and understand the chemistry of zeolite structures. Acknowledgment.Various polyviologen polyelectrolytes which may participate in photoinitiated electron-transfer reactions have been investigated as quenchers. A spectral study was made of the reduced polyviologen radicals on reducing the polyviologen species using the 2-propanol radical. Some of the mono radicals produced, possessing absorption spectra similar to that of the methylviologen radical cation, are found to produce multiradical species in the time scale of seconds and minutes. The nature of the final reduced products and the types of reactions generating them are discussed. The abilities of the polyviologens to quench the emission of the lowest excited states of the two photosensitizers, R~(bpy),(cN)~ and Ru(bpy)?+, were investigated together with the quantum yields of electron transfer and the rates of their back-reactions by using the laser flash photolysis technique. The highest yield of electron transfer was found for the Ru(bpy),2+-poly(o-xylylviologen) system where the quantum yield of photoinitiated electron transfer was determined to be 0.57. The results were compared to those obtained previously with methylviologen and other polymeric viologen systems. The higher than expected rates of quenching and back-reactions were attributed to hydrophobic interactions between the bipyridine groupings of the photosensitizer and quencher which may overcome the repulsive Coulombic forces between them.

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Section: Systems Containing R~( B P Y )~ ' Asmentioning

confidence: 49%

Charge separation in photoinitiated electron-transfer systems with polyviologen polyelectrolytes as quenchers

Gershuni¹,

Rabani²

1985

J. Phys. Chem.

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“…However, the pH used in the present system was 3.6, and the major ionizable groups in HA were undissociated. Therefore, the binding of Ru(bpy)3 2+ and MV 2+ with HA may be due to strong cooperative binding by the interaction of aromatic rings as well as anionic electrostatic forces, as reported for the case of PVS (30).…”

Section: Resultsmentioning

confidence: 61%

Photocatalytic Production of Hydrogen Peroxide by Tris(2,2‘-bipyridine) Ruthenium(II) Using Humic Acids as Electron Donor

Fukushima

Takagi

Tanaka

et al. 1998

Environ. Sci. Technol.

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The photosensitized production of H 2 O 2 by tris(2,2′-bipyridine) ruthenium(II) complex [Ru(bpy) 3 2+ ] was enhanced ∼120-fold by the presence of humic acid (HA). It was found that methyl viologen (MV 2+ ) as a redox mediator in this system was required to produce H 2 O 2 . Moreover, in the present system, H 2 O 2 was not produced in the absence of formic acid. The presumed role of formic acid is to reduce the oxidized HA. The reducing ability of HA assisted the photocatalytic reaction of Ru(bpy) 3 2+ . In addition, the results of the effect of inorganic salt on H 2 O 2 production suggest that the binding abilities of Ru(bpy) 3 2+ and MV 2+ with HA are determinant in the enhancement of H 2 O 2 production.

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“…It has been reported that neutral urea, which interacts through van der Waals and H-bonds, can also displace [Ru(bpy) 3 ] 2+ from PSS, 24 indicating the importance of non-coulombic interactions in this system. Similar behaviour was observed on addition of MgCl 2 ( Fig.…”

Section: Dppz]mentioning

confidence: 92%

“…The increases in luminescence intensity and lifetime observed when [Ru(bpy) 3 ] 2+ interacts with PSS 24,25,27 are attributed to binding in a less polar environment via a combination of electrostatic and hydrophobic interactions, lower local water activity, and reduced oxygen quenching (see below). Shielding [Ru(bpy) 3 ] 2+ from water enhances the luminescence quantum yield, 42 since the presence of water increases non-radiative decay.…”

Section: +mentioning

confidence: 99%

Influence of polystyrenesulfonate on electron transfer quenching of ruthenium trisbipyridine luminescence by viologens: non-covalent assembly and covalent tethering of the ruthenium complex

Tuite

Rose

Ennis³

et al. 2012

Phys. Chem. Chem. Phys.

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A new copolymer (RuB-PSS) of ruthenium(II)bis-(2,2 0 -bipyridine)(4-vinyl 2,2 0 -bipyridine) and styrene sulfonate was prepared which tethers the ruthenium chromophore directly to the polymer backbone. The photophysical properties of the copolymer, and its luminescence quenching by viologens, were compared with those of ruthenium (II) influence forward-and reverse-electron transfer reactions depending on the charge and hydrophobicity of the reactants. In the context of small molecule binding, we find that PSS provides a tenable model for DNA.

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The Interaction of the Tris(2,2′-bipyridine)ruthenium(II) Ion with Poly(p-styrenesulfonate)

Cited by 24 publications

References 12 publications

Charge separation in photoinitiated electron-transfer systems with polyviologen polyelectrolytes as quenchers

Charge separation in photoinitiated electron-transfer systems with polyviologen polyelectrolytes as quenchers

Photocatalytic Production of Hydrogen Peroxide by Tris(2,2‘-bipyridine) Ruthenium(II) Using Humic Acids as Electron Donor

Influence of polystyrenesulfonate on electron transfer quenching of ruthenium trisbipyridine luminescence by viologens: non-covalent assembly and covalent tethering of the ruthenium complex

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