Rhenium Hexanuclear Clusters: Bonding, Spectroscopy, and Applications of Molecular Chevrel Phases

Muñoz-Castro, Álvaro; Páez‐Hernández, Dayán; Arratia‐Pérez, Ramiro

doi:10.1007/430_2019_34

Cited by 2 publications

(3 citation statements)

References 72 publications

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“…The chemistry of chalcogenide-capped octahedral hexanuclear rhenium complexes with six terminal ligands has been well studied: 15 − 29 the complex has 24 d electrons (24e), and the oxidation state of each rhenium ion is +3. The complex unit is intriguing because it exhibits rich redox and photoluminescent properties.…”

Section: Introductionmentioning

confidence: 99%

“…The chemistry of chalcogenide-capped octahedral hexanuclear rhenium complexes with six terminal ligands has been well studied: − the complex has 24 d electrons (24e), and the oxidation state of each rhenium ion is +3. The complex unit is intriguing because it exhibits rich redox and photoluminescent properties. − ,− The terminal ligands on the complex are moderately inert to a substitution reaction, which results in stepwise ligand substitutions at the terminal positions. ,,, The complex unit undergoes one-electron oxidation, and the Re 6 (23e)/Re 6 (24e) process is dependent on the nature of the terminal ligands. ,,, The one-electron oxidation process of [Re 6 (μ 3 -S) 8 Cl 6 ] 4– (0.31 V vs Ag/AgCl) shifts positively upon substitution of the terminal chloride ligands with pyridine (py), leading to show at 0.77 V for trans -/ cis -[Re 6 (μ 3 -S) 8 Cl 4 (py) 2 ] 2– or 1.03 V for [Re 6 (μ 3 -S) 8 Cl 3 (py) 3 ] − . A trend similar to that mentioned above has also been observed for [Re 6 (μ 3 -S) 8 Cl 6– n (PEt 3 ) n ] n −4 (PEt 3 : triethylphosphine, n = 1–4) .…”

Section: Introductionmentioning

confidence: 99%

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Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands

et al. 2022

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The present study reports that the ground- and excited-state Re 6 (23e)/Re 6 (24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the N -heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions. Photoirradiation of [Re 6 (μ 3 -S) 8 Cl 6 ] 4– with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, [Re 6 (μ 3 -S) 8 Cl 5 (L)] 3– (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4′-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The bis- and tris-lut-substituted complexes, trans - and cis -[Re 6 (μ 3 -S) 8 Cl 4 (lut) 2 ] 2– and mer -[Re 6 (μ 3 -S) 8 Cl 3 (lut) 3 ] − , were synthesized by the reaction of [Re 6 (μ 3 -S) 8 Cl 6 ] 3– with an excess amount of lut in refluxed N , N -dimethylformamide. The mono-L-substituted complexes showed one-electron redox processes assignable to E 1/2 [Re 6 (23e)/Re 6 (24e)] = 0.49–0.58 V versus Ag/AgCl. The ground-state oxidation potentials were linearly correlated with the p K a of the N-heteroaromatic ligand [p K a (L)], the 1 H NMR chemical shift of the ortho proton on the coordinating ligand, and the Hammett constant (σ) of the pyridyl-ligand substituent. The series of [Re 6 (μ 3 -S) 8 X 6– n (L) n ] n −4 complexes ( n = 0, X = Cl, Br, I, or NCS; n = 1–3, X = Cl) showed a linear correlation with the sum of the Lever electrochemical parameters at the six terminal ligands (Σ E L ). The cyclic voltammograms of the mono-L-substituted complexes (L = bpy, cpy, and pz) showed one-electron redox waves assignable to E 1/2 (L 0 /L – ) = −1.28 to −1.48 V versus Ag/AgCl. Two type...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands

et al. 2022

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“…The inclusion of metal centers possessing catalytic, photosensitizing, or other properties in the structure expands the capabilities of such frameworks. − In this work, octahedral chalcogenide rhenium cluster complexes [{Re 6 Q i 8 }L a 6 ] (Q = S, Se; L = organic or inorganic ligand) are considered to be such functional metalloligand centers. The works of recent decades related to cluster chemistry have shown both a sufficiently simple chemical modification of the apical ligand environment − and a number of useful physicochemical properties: luminescence, , X-ray contrast, redox, , etc. − Despite the large number of studies on rhenium cluster compounds, − only a few works in which clusters act as secondary building blocks are known in the literature. The work in ref describes the preparation of honeycomb-like tubular self-assembly frameworks based on neutral fac -[{Re 6 Q i 7 Br i }(pyz) a 3 Br a 3 ] (Q = S, Se; pyz = pyrazine).…”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Microporous M-HOFs Based on an Octahedral Rhenium Cluster with Benzimidazole

et al. 2021

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Substitution of apical halide ligands in [{Re6Sei 8}Xa 6]3– (X = Cl, Br) by benzimidazole (bimzH) accompanied by a self-assembly process leads to the formation of microporous Re6-based hydrogen-bonded organic frameworks (Re6-HOFs) constructed on N–H···X hydrogen bonds and π–π-stacking interactions between bimzH ligands. Re6-HOFs demonstrate sorption properties with a Brunauer–Emmett–Teller surface area of up to 443 m2 g–1 and luminescence with a quantum yield and an emission lifetime of up to 0.16 and 16 μs, respectively. The compounds obtained complement small groups of transition-metal cluster-based HOFs, which are a perspective for the development of multifunctional frameworks.

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Rhenium Hexanuclear Clusters: Bonding, Spectroscopy, and Applications of Molecular Chevrel Phases

Cited by 2 publications

References 72 publications

Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands

Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands

Self-Assembled Microporous M-HOFs Based on an Octahedral Rhenium Cluster with Benzimidazole

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