Synthesis, Structure, and Physicochemical  Properties of Molecular Rhenium Cluster  Complexes With 4-Phenylpyridine Molecules  as Terminal Ligands

Ulantikov, Anton A.; Gayfulin, Yakov M.; Sukhikh, Taisiya S.; Ryadun, Alexey A.; Ryzhikov, Maxim R.; Mironov, Yu. V.

doi:10.1134/s0022476621070040

Cited by 8 publications

(10 citation statements)

References 40 publications

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“…Various neutral and anionic ligands have been introduced at the six terminal positions of sulfide-capped octahedral hexanuclear rhenium(III) complexes by thermal substitution reactions of the terminal halides or hydroxides in [Re 6 (μ 3 -S) 8 X 6 ] 4– (X = Cl, Br, I, OH) in solution or under melt conditions (see refs ( 16 , 35 , 37 , 39 , 44 , 45 , 47 − 49 , 52 − 54 , 56 − 58 , 61 , 63 , 65 − 67 , 70 , 71 , 75 , 76 , 83 − 88 )). To our knowledge, several reports have been published on photosubstitution reactions of octahedral hexanuclear metal complexes.…”

Section: Resultsmentioning

confidence: 99%

“…The complex unit is intriguing because it exhibits rich redox and photoluminescent properties. 16 − 20 , 28 − 75 The terminal ligands on the complex are moderately inert to a substitution reaction, which results in stepwise ligand substitutions at the terminal positions. 35 , 51 , 76 , 77 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.…”

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%

“…Sulfide-capped octahedral hexanuclear rhenium(III) complexes exhibit photoluminescence in the solid state and in solution. ,− ,− ,,,− ,− ,,,,− ,− , The photoemissive excited triplet states of these complexes can be classified into two types: cluster core-centered ( 3 CC) and cluster core-to-L charge-transfer [more generally metal-to-ligand charge-transfer ( 3 MLCT)] states. Most octahedral hexanuclear complexes generate the relevant 3 CC states upon photoexcitation.…”

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: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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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“…It has been found that the use of molten organic compounds as a reaction media leads to different products from these reactions depending on type of the compound used. As a rule, aprotic compounds lead to the formation of electrically neutral molecular clusters [Re 6 Q 8 X 2 L 4 ] [12,29,30]. At the same time, melts of protonic proligands often give completely substituted homoleptic products [Re 6 Q 8 L 6 ] n [31][32][33].…”

Section: Synthesismentioning

confidence: 99%

Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN− Apical Ligands

et al. 2021

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The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes trans-[Re6S8(bpy)4(CN)2] and trans-[Re6S8(bpy)2(CN)4]2− (bpy = 4,4′-bipyridine) obtained by reactions of corresponding hexarhenium cyanohalides with molten bpy are reported. The complexes were crystallized as solvates, displaying supramolecular structures based on cluster units linked by numerous weak interactions with bpy molecules. The molecular compound trans-[Re6S8(bpy)4(CN)2] (1) is insoluble in water and common organic solvents, while the ionic compound trans-Cs1.7K0.3[Re6S8(bpy)2(CN)4] (2) is somewhat soluble in DMSO, DMF and N-methylpyrrolidone. The presence of the redox-active ligand bpy leads to the occurrence of multi-electron reduction transitions in a solution of 2 at moderate potential values. The ambidentate CN− ligand is the secondary functional group, which has potential for the synthesis of coordination polymers based on the new cluster complexes. In addition, both new compounds show a weak red luminescence, which is characteristic of complexes with a {Re6S8}2+ cluster core.

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Octahedral Hexanuclear Rhenium Cluster Dimers Bridged by Pyrazine or 4,4′-Bipyridine with 23- and 24-Electron Configurations

Yoshimura,

Nagata,

Nakano

2024

Inorg. Chem.

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New pyrazine (pz)-and 4,4′-bipyridine (4,4′-bpy)bridged octahedral hexanuclear rhenium(III) cluster dimers, [{Re 6 (μ 3 -S) 8 Cl 5 } 2 (μ-L)] 6− (L = pz, [1] 6− ; L = 4,4′-bpy, [2] 6− ), with 2 × 24 d-electrons {Re 6 (24e)} 2 were obtained in a single-step reaction via photoirradiation of [Re 6 (μ 3 -S) 8 Cl 6 ] 4− with L in a 2:1 ratio at room temperature. The {Re 6 (23e)} 2 dimers, [{Re 6 (μ 3 -S) 8 Cl 5 } 2 (μ-L)] 4− (L = pz, [1′] 4− ; L = 4,4′-bpy, [2′] 4− ), were synthesized through two-electron oxidation of [1] 6− and [2] 6− , respectively. The single-crystal X-ray structures of [1] 6− and [1′] 4− were determined, revealing structural distortion of the Re 6 core of [1′] 4− due to the Jahn−Teller effect. The cyclic voltammograms of [1] 6− and [2] 6− showed two steps of one-electron redox processes attributable to Re 6 (23e)Re 6 (24e)/{Re 6 (24e)} 2 and {Re 6 (23e)} 2 / Re 6 (23e)Re 6 (24e), respectively. The separation between the two redox potentials is small (0.056 V for [1] 6− and 0.039 V for [2] 6− ). The magnetic susceptibilities of [1′] 4− and [2′] 4− were almost temperature-independent, with values of 2.98 and 2.85 μ B , respectively, indicating paramagnetism. These results suggest weak electronic interaction between two cluster units bridged by pz or 4,4′-bpy in the intercluster mixed valence state. The compounds [1] 6− and [2] 6− show photoluminescence in the near-infrared region at 296 K in the solid state.

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Synthesis, Structure, and Physicochemical Properties of Molecular Rhenium Cluster Complexes With 4-Phenylpyridine Molecules as Terminal Ligands

Cited by 8 publications

References 40 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

Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN− Apical Ligands

Octahedral Hexanuclear Rhenium Cluster Dimers Bridged by Pyrazine or 4,4′-Bipyridine with 23- and 24-Electron Configurations

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