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A comparative study of the redox and excited state properties of (nBu4N)2[Mo6X14] and (nBu4N)2[Mo6X8(CF3COO)6] (X = Cl, Br, or I)
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SYSNO ASEP 0392093 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title A comparative study of the redox and excited state properties of (nBu4N)2[Mo6X14] and (nBu4N)2[Mo6X8(CF3COO)6] (X = Cl, Br, or I) Author(s) Kirakci, Kaplan (UACH-T) SAI, RID, ORCID
Kubát, Pavel (UFCH-W) RID, ORCID, SAI
Langmaier, Jan (UFCH-W) RID, ORCID, SAI
Polívka, T. (CZ)
Fuciman, M. (CZ)
Fejfarová, Karla (FZU-D)
Lang, Kamil (UACH-T) SAI, RID, ORCIDSource Title Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 42, č. 19 (2013), s. 7224-7232Number of pages 9 s. Language eng - English Country GB - United Kingdom Keywords HEXANUCLEAR MOLYBDENUM CLUSTERS ; TRANSITION-METAL CLUSTERS ; PHOTOPHYSICAL PROPERTIES ; CHLORIDE CLUSTERS Subject RIV CA - Inorganic Chemistry Subject RIV - cooperation J. Heyrovsky Institute of Physical Chemistry - Physical ; Theoretical Chemistry R&D Projects GA13-05114S GA ČR - Czech Science Foundation (CSF) Institutional support UACH-T - RVO:61388980 ; UFCH-W - RVO:61388955 ; FZU-D - RVO:68378271 UT WOS 000317981700061 EID SCOPUS 84876929197 DOI 10.1039/c3dt32863e Annotation The excited-state dynamics, luminescence, and redox properties of a series of hexanuclear molybdenum cluster complexes, (nBu4N)2[Mo6X14] and (nBu4N)2[Mo6X8(CF3COO)6] (X = Cl, Br, or I), were investigated. Substitution of the apical halogen ligands for the trifluoroacetate ligands increased the oxidation potentials and induced a blue shift in the absorption and luminescence bands as well as a considerable increase in the luminescence quantum yields for heavy inner ligands. Time-resolved transient absorption measurements showed that the intersystem crossing from the excited singlet states is ultrafast with time constants ranging between <120 fs and 1.68 ps and leads to hot triplet states. The following cooling occurred at a ps time scale and was assigned to electronic redistribution within the emissive triplet state sublevels. The formation of singlet oxygen, O2(1Δg), suggested earlier on the basis of photooxidation experiments for some complexes, was revised by direct measurements of O2(1Δg) phosphorescence. We showed the effects of the attached ligands on key physico-chemical and photophysical parameters of the title complexes. The synthesis and structural characterisation of a new cluster complex, (nBu4N)2[Mo6Br8(CF3COO)6], completed the series. Our results demonstrated that the complexes with heavy inner ligands (Br, I) and apical trifluoroacetate ligands were photochemically and electrochemically stable, highly luminescent, and good sensitisers of O2(1Δg). Workplace Institute of Inorganic Chemistry Contact Jana Kroneislová, krone@iic.cas.cz, Tel.: 311 236 931 Year of Publishing 2014
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