Cation effect on the quenching of the photoexcited state of tetrakis(μ-pyrophosphito-P,P′)diplatinate(II) by octacyanomolybdate(IV) in aqueous solution

Tadashi Yamaguchi, Yoichi Sasaki

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Abstract

The photoquenching reaction of [Pt2(pop)4]4- (pop2- = pyrophosphite(2-)) with [Mo(CN)8]4- was studied in 0.01 M HCl or HClO4 in the presence of various added electrolytes (0.49 M) (LiCl, NaCl, KCl, CsCl, NH4Cl, (C2H5)4NCl, and NaClO4) at 25°C. The quenching rate constants (kq,) differ by nearly 1 order of magnitude from 1.17 × 107 (LiCl) to 9.90 × 107 M-1 s-1 (CsCl). The phosphorescence lifetime (τ0) in the absence of the quencher is practically constant (8.3-8.6 μs) regardless of the type of electrolyte added. kq shows a linear correlation with the reciprocal of the cation Stokes radii except for the case of (C2H5)4N+. The cation effect was interpreted by considering a precursor ion triplet among two negatively charged reactants and a foreign cation. The role of the cation is to reduce the Coulombic barrier of the two reactants in order to form an encounter complex.

Original languageEnglish
Pages (from-to)493-495
Number of pages3
JournalInorganic Chemistry
Volume29
Issue number3
Publication statusPublished - 1990
Externally publishedYes

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Cations
Quenching
quenching
aqueous solutions
cations
Electrolytes
electrolytes
Phosphorescence
phosphorescence
encounters
Rate constants
Ions
life (durability)
radii
ions
cesium chloride

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Cation effect on the quenching of the photoexcited state of tetrakis(μ-pyrophosphito-P,P′)diplatinate(II) by octacyanomolybdate(IV) in aqueous solution",
abstract = "The photoquenching reaction of [Pt2(pop)4]4- (pop2- = pyrophosphite(2-)) with [Mo(CN)8]4- was studied in 0.01 M HCl or HClO4 in the presence of various added electrolytes (0.49 M) (LiCl, NaCl, KCl, CsCl, NH4Cl, (C2H5)4NCl, and NaClO4) at 25°C. The quenching rate constants (kq,) differ by nearly 1 order of magnitude from 1.17 × 107 (LiCl) to 9.90 × 107 M-1 s-1 (CsCl). The phosphorescence lifetime (τ0) in the absence of the quencher is practically constant (8.3-8.6 μs) regardless of the type of electrolyte added. kq shows a linear correlation with the reciprocal of the cation Stokes radii except for the case of (C2H5)4N+. The cation effect was interpreted by considering a precursor ion triplet among two negatively charged reactants and a foreign cation. The role of the cation is to reduce the Coulombic barrier of the two reactants in order to form an encounter complex.",
author = "Tadashi Yamaguchi and Yoichi Sasaki",
year = "1990",
language = "English",
volume = "29",
pages = "493--495",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "3",

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TY - JOUR

T1 - Cation effect on the quenching of the photoexcited state of tetrakis(μ-pyrophosphito-P,P′)diplatinate(II) by octacyanomolybdate(IV) in aqueous solution

AU - Yamaguchi, Tadashi

AU - Sasaki, Yoichi

PY - 1990

Y1 - 1990

N2 - The photoquenching reaction of [Pt2(pop)4]4- (pop2- = pyrophosphite(2-)) with [Mo(CN)8]4- was studied in 0.01 M HCl or HClO4 in the presence of various added electrolytes (0.49 M) (LiCl, NaCl, KCl, CsCl, NH4Cl, (C2H5)4NCl, and NaClO4) at 25°C. The quenching rate constants (kq,) differ by nearly 1 order of magnitude from 1.17 × 107 (LiCl) to 9.90 × 107 M-1 s-1 (CsCl). The phosphorescence lifetime (τ0) in the absence of the quencher is practically constant (8.3-8.6 μs) regardless of the type of electrolyte added. kq shows a linear correlation with the reciprocal of the cation Stokes radii except for the case of (C2H5)4N+. The cation effect was interpreted by considering a precursor ion triplet among two negatively charged reactants and a foreign cation. The role of the cation is to reduce the Coulombic barrier of the two reactants in order to form an encounter complex.

AB - The photoquenching reaction of [Pt2(pop)4]4- (pop2- = pyrophosphite(2-)) with [Mo(CN)8]4- was studied in 0.01 M HCl or HClO4 in the presence of various added electrolytes (0.49 M) (LiCl, NaCl, KCl, CsCl, NH4Cl, (C2H5)4NCl, and NaClO4) at 25°C. The quenching rate constants (kq,) differ by nearly 1 order of magnitude from 1.17 × 107 (LiCl) to 9.90 × 107 M-1 s-1 (CsCl). The phosphorescence lifetime (τ0) in the absence of the quencher is practically constant (8.3-8.6 μs) regardless of the type of electrolyte added. kq shows a linear correlation with the reciprocal of the cation Stokes radii except for the case of (C2H5)4N+. The cation effect was interpreted by considering a precursor ion triplet among two negatively charged reactants and a foreign cation. The role of the cation is to reduce the Coulombic barrier of the two reactants in order to form an encounter complex.

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M3 - Article

VL - 29

SP - 493

EP - 495

JO - Inorganic Chemistry

JF - Inorganic Chemistry

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