Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

Olga A. Efremova; Yuri A. Vorotnikov; Konstantin A. Brylev; Natalya A. Vorotnikova; Igor N. Novozhilov; Natalia V. Kuratieva; Mariya V. Edeleva; David M. Benoit; Noboru Kitamura; Yuri V. Mironov; Michael A. Shestopalov; Andrew J. Sutherland

doi:10.1039/c6dt02863b

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

Olga A. Efremova^*, Yuri A. Vorotnikov, Konstantin A. Brylev, Natalya A. Vorotnikova, Igor N. Novozhilov, Natalia V. Kuratieva, Mariya V. Edeleva, David M. Benoit, Noboru Kitamura, Yuri V. Mironov, Michael A. Shestopalov, Andrew J. Sutherland

^*Corresponding author for this work

Chemical Engineering & Applied Chemistry

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Abstract

This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (ⁿBu₄N)₂[{Mo₆X₈}(OTs)₆] and (ⁿBu₄N)₂[{Mo₆X₈}(PhSO₃)₆] (where X^- is Cl^-, Br^- or I^-; OTs^- is p-toluenesulfonate and PhSO₃ ^- is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo₆I₈}⁴⁺ cluster core. Moreover, cyclic voltammetric studies revealed that (ⁿBu₄N)₂[{Mo₆X₈}(OTs)₆] and (ⁿBu₄N)₂[{Mo₆X₈}(PhSO₃)₆] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (ⁿBu₄N)₂[{Mo₆X₈}X₆].

Original language	English
Pages (from-to)	15427-15435
Number of pages	9
Journal	Dalton Transactions
Volume	45
Issue number	39
Early online date	30 Aug 2016
DOIs	https://doi.org/10.1039/c6dt02863b
Publication status	Published - 21 Oct 2016

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Octahedral molybdenum cluster complexes with aromatic sulfonate ligands
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title = "Octahedral molybdenum cluster complexes with aromatic sulfonate ligands",

abstract = "This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].",

author = "Efremova, {Olga A.} and Vorotnikov, {Yuri A.} and Brylev, {Konstantin A.} and Vorotnikova, {Natalya A.} and Novozhilov, {Igor N.} and Kuratieva, {Natalia V.} and Edeleva, {Mariya V.} and Benoit, {David M.} and Noboru Kitamura and Mironov, {Yuri V.} and Shestopalov, {Michael A.} and Sutherland, {Andrew J.}",

note = "This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.",

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doi = "10.1039/c6dt02863b",

language = "English",

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T1 - Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

AU - Efremova, Olga A.

AU - Vorotnikov, Yuri A.

AU - Brylev, Konstantin A.

AU - Vorotnikova, Natalya A.

AU - Novozhilov, Igor N.

AU - Kuratieva, Natalia V.

AU - Edeleva, Mariya V.

AU - Benoit, David M.

AU - Kitamura, Noboru

AU - Mironov, Yuri V.

AU - Shestopalov, Michael A.

AU - Sutherland, Andrew J.

N1 - This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

PY - 2016/10/21

Y1 - 2016/10/21

N2 - This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].

AB - This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].

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Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

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