The Octahedral M6Y8 And M6Y12 Clusters of Group 4 and 5 Transition Metals

Prokopuk, Nicholas; Shriver, Duward F.

doi:10.1016/s0898-8838(08)60148-8

Cited by 91 publications

(56 citation statements)

References 152 publications

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“…Octahedral halide clusters of molybdenum(II) with the general formula [{Mo 6 (μ 3 -X) 8 }L 6 ] n (X = Cl – , Br – , I – ; L = inorganic or organic ligands; {Mo 6 (μ 3 -X) 8 } 4+ is the cluster core) emit relatively long-lived (some tens or even hundreds of microseconds!) red phosphorescence, which can be used for energy transformation and photooxidation, generation of singlet oxygen, as well as for sensing .…”

Section: Introductionmentioning

confidence: 99%

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

et al. 2016

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The reactions between the tetra-n-butylammonium salt of [{Mo6I8}I6](2-) and silver carboxylates RCOOAg (R = CH3 (1), C(CH3)3 (2), α-C4H3O (3), C6H5 (4), α-C10H7 (5), or C2F5 (6)) in CH2Cl2 afforded new carboxylate complexes [{Mo6I8}(RCOO)6](2-). The complexes were characterized by X-ray single-crystal diffraction and elemental analysis, cyclic/differential pulse voltammetry, and IR, NMR, and UV-visible spectroscopies. The emission properties of the complexes 1-6, and those of the earlier reported complexes with R = CF3 (7) and n-C3F7 (8), were studied both in acetonitrile solution and in the solid state. In deaerated CH3CN at 298 K, all of the complexes 1-8 exhibit intense and long-lived emission with the quantum yield and lifetime being 0.48-0.73 and 283-359 μs, respectively. The oxidation (Eox)/reduction (Ered) potentials of the complexes correlate linearly with the pKa value of the terminal carboxylate ligands L = RCOO (pKa(L)). Reflecting the pKa(L) dependences of Eox/Ered, the emission energy (νem) of the complexes was also shown to correlate with pKa(L). The present study successfully demonstrates synthetic tuning of the redox, spectroscopic, and photophysical characteristics of a {Mo6I8}(4+)-based cluster complex with pKa(L).

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Section: Introductionmentioning

confidence: 99%

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

et al. 2016

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“…The discrete {Ta 6 Br 12 } species are highly interesting because of their ultra-small size ( ca . 1 nm) and the distinct electronic structure brought by the coexistence of metal-metal and covalent bonds, while they also bear the starting point of various solution based chemical/physical reactions to obtain various kinds of [{Ta 6 Br i 12 }L a 6 ] derivatives [7, 10, 16, 17, 18, 19]. Moreover, the electronic structure of discrete {Ta 6 Br 12 } species endows their variable optical property, depending on both the oxidation state of {Ta 6 Br 12 } (2+, 3+ or 4+) and the properties of apical ligands –thus they can be used as the dye for transparent optical devices [5, 6, 20, 21, 22].…”

Section: Introductionmentioning

confidence: 99%

Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method

Chen

Wilmet

Truong

et al. 2018

Heliyon

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Hexanuclear tantalum bromide cluster units [{Ta6Bri12}La6] (i = inner, a = apical, L = ligand OH or H2O) are embedded into SiO2 nanoparticles by a reverse microemulsion (RM) based method. [{Ta6Bri12}Bra2 (H2O)a4]·nH2O (noted TBH) and tetraethyl orthosilicate (TEOS) are used as the starting cluster compound and the precursor of SiO2, respectively. The RM system in this study consists of the n-heptane (oil phase), Brij L4 (surfactants), ethanol, TEOS, ammonia solution and TBH aqueous sol. The size and morphology of the product namely {Ta6Br12}@SiO2 nanoparticles are analyzed by HAADF-STEM and EDS mappings. The presence and integrity of {Ta6Br12} in the SiO2 nanoparticles are evidenced by EDS mapping, ICP-OES/IC and XPS analysis. The optical properties of {Ta6Br12}@SiO2 nanoparticles are analyzed by diffuse reflectance UV-vis spectroscopy, further evidencing the integrity of the embedded {Ta6Br12} and revealing their oxidation state. Both {Ta6Br12}2+ and {Ta6Br12}3+ are found in SiO2 nanoparticles, but the latter is much more stable than the former. The by-products in this RM-based synthesis, as well as their related factors, are also discussed.

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“…Octahedral halide cluster complexes of Mo II and W II , [{M 6 (µ 3 ‐X) 8 }L 6 ] (M = Mo or W; X = Cl, Br or I; L = neutral or anionic ligands), are chemically robust constructions with outstanding photophysical properties; therefore, they are potentially useful for various applications . The most studied are the derivatives of molybdenum chloride and bromide (M = Mo; X = Cl, Br).…”

Section: Introductionmentioning

confidence: 99%

Complexes of {W₆I₈}⁴⁺ Clusters with Carboxylates: Preparation, Electrochemistry, and Luminescence

et al. 2017

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The reactions between (Bu4N)2[{W6I8}I6] (1) and silver carboxylates RCOOAg in CH2Cl2 afforded new luminescent carboxylate complexes (Bu4N)2[{W6I8}(RCOO)6] [R = CH3 (2), C6H5 (3), C2F5 (4), C3F7 (5), C6F5 (6)]. The complexes were characterized by single‐crystal X‐ray diffraction, elemental analysis, cyclic voltammetry, and IR and NMR spectroscopy. Complexes 1–6 all exhibit intense and long‐lived photoluminescence. The carboxylate complexes undergo reversible electrochemical oxidation in two consecutive one‐electron steps.

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The Octahedral M6Y8 And M6Y12 Clusters of Group 4 and 5 Transition Metals

Cited by 91 publications

References 152 publications

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method

Complexes of {W₆I₈}⁴⁺ Clusters with Carboxylates: Preparation, Electrochemistry, and Luminescence

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The Octahedral M6Y8 And M6Y12 Clusters of Group 4 and 5 Transition Metals

Cited by 91 publications

References 152 publications

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo6I8}4+ Core Cluster Complexes by Terminal Carboxylate Ligands

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo6I8}4+ Core Cluster Complexes by Terminal Carboxylate Ligands

Embedding hexanuclear tantalum bromide cluster {Ta6Br12} into SiO2 nanoparticles by reverse microemulsion method

Complexes of {W6I8}4+ Clusters with Carboxylates: Preparation, Electrochemistry, and Luminescence

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Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

Synthetic Tuning of Redox, Spectroscopic, and Photophysical Properties of {Mo₆I₈}⁴⁺ Core Cluster Complexes by Terminal Carboxylate Ligands

Complexes of {W₆I₈}⁴⁺ Clusters with Carboxylates: Preparation, Electrochemistry, and Luminescence