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Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

DOIFull Paper Access

75

Citations

44

References

2016

Year

Olga A. Efremova, Yuri A. Vorotnikov, Konstantin A. Brylev, Natalya A. Vorotnikova, Igor N. Novozhilov, Natalia V. Kuratieva, Mariya Edeleva, David M. Benoit, Noboru Kitamura, Yuri V. Mironov,
Dalton Transactions

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 (<sup>n</sup>Bu<sub>4</sub>N)<sub>2</sub>[{Mo<sub>6</sub>X<sub>8</sub>}(OTs)<sub>6</sub>] and (<sup>n</sup>Bu<sub>4</sub>N)<sub>2</sub>[{Mo<sub>6</sub>X<sub>8</sub>}(PhSO<sub>3</sub>)<sub>6</sub>] (where X<sup>-</sup> is Cl<sup>-</sup>, Br<sup>-</sup> or I<sup>-</sup>; OTs<sup>-</sup> is p-toluenesulfonate and PhSO<sub>3</sub><sup>-</sup> 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 {Mo<sub>6</sub>I<sub>8</sub>}<sup>4+</sup> cluster core. Moreover, cyclic voltammetric studies revealed that (<sup>n</sup>Bu<sub>4</sub>N)<sub>2</sub>[{Mo<sub>6</sub>X<sub>8</sub>}(OTs)<sub>6</sub>] and (<sup>n</sup>Bu<sub>4</sub>N)<sub>2</sub>[{Mo<sub>6</sub>X<sub>8</sub>}(PhSO<sub>3</sub>)<sub>6</sub>] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (<sup>n</sup>Bu<sub>4</sub>N)<sub>2</sub>[{Mo<sub>6</sub>X<sub>8</sub>}X<sub>6</sub>].

References

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