Excited singlet states of molybdenum chloride clusters

Strauß, Uwe; Perchenek, N.; Rühle, W. W.; Queisser, H. J.; Simon, Arndt

doi:10.1016/0009-2614(93)90063-7

Cited by 3 publications

(4 citation statements)

References 11 publications

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“…The presented results contradict the luminescence picosecond data obtained on single crystals of (Bu 4 N) 2 [Mo 6 Cl 14 ]. 26 The observed emission with a time constant of 630 ps at 290 K was attributed to the emission from the excited singlet states. Based on our absorption measurements, we cannot confirm long-lived singlet states in the acetonitrile solutions.…”

Section: Dalton Transactions Papermentioning

confidence: 93%

“…The difference between our results and those reported in ref. 26 may be related to the fact that experiments in solution provide information about the behaviour of individual molecules, whereas crystals are essentially infinite systems of molecules that may have additional states not existing in the spectra of individual molecules.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

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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)

et al. 2013

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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((1)Δg), suggested earlier on the basis of photooxidation experiments for some complexes, was revised by direct measurements of O2((1)Δg) 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((1)Δg).

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Section: Dalton Transactions Papermentioning

confidence: 93%

Section: Dalton Transactions Papermentioning

confidence: 99%

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)

et al. 2013

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“…Octahedral molybdenum halide cluster compounds based on the [Mo 6 X 14 ] 2– ion exhibit remarkable photophysical and photochemical properties because they show photoluminescence properties in solid state and in solution with typical emissions in the red to infra‐red region with high quantum yields, plus excellent potential in the generation of singlet oxygen 1–8…”

Section: Introductionmentioning

confidence: 99%

Molecular Oxygen Modulated Luminescence of an Octahedro‐hexamolybdenum Iodide Cluster having Six Apical Thiocyanate Ligands

Riehl

Ströbele

Enseling

et al. 2016

Zeitschrift anorg allge chemie

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The synthesis, characterization, and luminescence properties of (Bu4N)2[Mo6I8(NCS)6] are reported. Orange crystals of (Bu4N)2[Mo6I8(NCS)6] were crystallized from acetone solution and used for X‐ray single‐crystal structure determination and refinement, yielding a structure with a centrosymmetric [Mo6I8(NCS)6]2– ion. Photoluminescence studies on the crystalline solid revealed a broad excitation in the UV/Vis region and an emission around 690 nm. The red emission intensity decreases with increasing partial pressure of atmospheric molecular O2.

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“…For more than two decades, the rich photophysical and photochemical properties of transition metal cluster compounds have sustained the interest of chemists and physicists who study them. , Related extended network compounds possessing polynuclear clusters as their principle structural feature are the superconducting Chevrel phases PbMo 6 Q 8 (Q = S, Se, Te). − Discrete M 6 (μ 3 -Q) 8 L 6 include the intensely luminescent hexanuclear molybdenum(II) and tungsten(II) halide clusters [M 6 (μ 3 -X) 8 X‘ 6 ] 2- (M = Mo, W; X, X‘ = Cl, Br, I), which have been extensively studied. − The latter clusters are comprised of six metal atoms arranged in an octahedral core, with eight face-capping halides and six terminal donor ligands. These compounds display long-lived excited states and undergo facile ground- and excited-state multielectron transfer by electrogenerated chemiluminescence. − Such properties offer the potential for these clusters to play a central role in light-induced chemical reactions and optically based sensors. − …”

Section: Introductionmentioning

confidence: 99%

Electronic Transitions in [Re₆S₈X₆]⁴^- (X = Cl, Br, I): Results from Time-Dependent Density Functional Theory and Solid-State Calculations

Roy

Hughbanks

2006

Inorg. Chem.

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Relativistic time-dependent density functional theory (TDDFT) calculations were performed on the excited states of the [Re6S8X6](4-) (X = Cl, Br, I) series. For all members of the series, the lowest excited states in the spectra do not correspond to a ligand-to-metal (or ligand-to-cluster) excitation but rather a cluster-cluster transition from the HOMO e(g) to antibonding t(1u) orbitals with only a modest admixture of Re-X sigma* character. These results lead to a re-evaluation of the role of the axial ligand in these compounds. The calculated excitation energies reproduce the experimental absorption and emission spectra. This work also confirms previous TDDFT calculations on the emission energies. Results for discrete cluster ions are compared with those obtained from calculations in the solid state in Cs4[Re6S8X6].CsX (X = Cl, Br) and Cs4[Re6S8I6].2CsI. Significant differences are seen in the relatively higher energies of the antibonding t(1u) orbital in the solid-state case, and an inversion in the orbital character of the two allowed absorptions is calculated. The e(g) (HOMO)-to-a(2g) (LUMO) orbital energy differences corresponding to the emission transition are quite comparable for the solid state and discrete cluster calculations, and both overestimate the observed emission energy by the same margin.

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Excited singlet states of molybdenum chloride clusters

Cited by 3 publications

References 11 publications

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)

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)

Molecular Oxygen Modulated Luminescence of an Octahedro‐hexamolybdenum Iodide Cluster having Six Apical Thiocyanate Ligands

Electronic Transitions in [Re₆S₈X₆]⁴^- (X = Cl, Br, I): Results from Time-Dependent Density Functional Theory and Solid-State Calculations

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Excited singlet states of molybdenum chloride clusters

Cited by 3 publications

References 11 publications

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)

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)

Molecular Oxygen Modulated Luminescence of an Octahedro‐hexamolybdenum Iodide Cluster having Six Apical Thiocyanate Ligands

Electronic Transitions in [Re6S8X6]4- (X = Cl, Br, I): Results from Time-Dependent Density Functional Theory and Solid-State Calculations

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Electronic Transitions in [Re₆S₈X₆]⁴^- (X = Cl, Br, I): Results from Time-Dependent Density Functional Theory and Solid-State Calculations