Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

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

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].

Citation

Efremova, O. A., Vorotnikov, Y. A., Brylev, K. A., Vorotnikova, N. A., Novozhilov, I. N., Kuratieva, N. V., Edeleva, M. V., Benoit, D. M., Kitamura, N., Mironov, Y. V., Shestopalov, M. A., & Sutherland, A. J. (2016). Octahedral molybdenum cluster complexes with aromatic sulfonate ligands. Dalton Transactions : an international journal of inorganic chemistry, 45(39), 15427-15435. https://doi.org/10.1039/c6dt02863b

• Acceptance Date: Aug 30, 2016
• Publication Date: Aug 30, 2016
• Deposit Date: Sep 7, 2016
• Publicly Available Date: Sep 7, 2016
• Journal: Dalton transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 45
• Issue: 39
• Pages: 15427-15435
• DOI: https://doi.org/10.1039/c6dt02863b
• Keywords: Octahedral molybdenum cluster complexes
• Public URL: https://hull-repository.worktribe.com/output/442801
• Publisher URL: http://pubs.rsc.org/en/content/articlelanding/2016/dt/c6dt02863b#!divAbstract
• Additional Information: : This document is Similarity Check deposited; : Supplementary Information; : Crystal Structure Data; : Michael A. Shestopalov (ORCID); : Michael A. Shestopalov (ResearcherID); : The Royal Society of Chemistry has an exclusive publication licence for this journal; OPEN ACCESS: This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0); : Single-blind; : Received 19 July 2016; Accepted 30 August 2016; Accepted Manuscript published 30 August 2016; Advance Article published 7 September 2016; Version of Record published 4 October 2016
• Contract Date: Sep 7, 2016