Supramolecular Frameworks Based on Rhenium Clusters Using the Synthons Approach

Audebrand, Nathalie; Demont, Antoine; Osta, Racha El; Mironov, Yuri V.; Наумов, Н. Г.; Cordier, Stéphane

doi:10.3390/molecules26092662

“…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%

“…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 , , , , , , − , − , − , , , − , , , , , − ). To our knowledge, several reports have been published on photosubstitution reactions of octahedral hexanuclear metal complexes. ,,− Gray et al reported that the emission lifetime (τ em ) and quantum yield (Φ em ) of a hexanuclear rhenium complex with terminal iodides or solvent molecules in dichloromethane increase in the presence of an added iodide ion or neat solvent molecules [i.e., dimethyl sulfoxide (DMSO)], suggesting the labile nature of the terminal halides in the excited state. , Zheng et al reported that UV irradiation of [Re 6 (μ 3 -Se) 8 (PEt 3 ) 5 {HNC(OCH 3 ) (CH 3 )}] 2+ in acetonitrile produces [Re 6 (μ 3 -Se) 8 (CH 3 CN) (PEt 3 ) 5 ] 2+ and that of a dichloromethane solution of [Re 6 (μ 3 -Se) 8 (CO)(PEt 3 ) 5 ] 2+ affords a 23e complex, [Re 6 (μ 3 -Se) 8 Cl(PEt 3 ) 5 ] 2+ , in which the coordinating chloride ion originates from dichloromethane. , Szczepura et al reported oxazoline and oxazine ligand removal reactions on [Re 6 (μ 3 -Se 8 ) (PEt 3 ) 5 (L)] 2+ (L = 2-methyloxazoline, 2-phenyloxazoline, and 2-methyloxazine) by UV irradiation .…”

Section: Resultsmentioning

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

Yoshimura

¹

,

Nishizawa

²

,

Nagata

³

et al. 2022

ACS Omega

7

0

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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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Playing with [{Mo₆Brⁱ₆Seⁱ₂}(CN)^a₆]⁴⁻ Cluster Building Blocks and Mn(salen)⁺ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

Cordier

¹

,

Daigre

²

,

Tarasenko

³

et al. 2023

Zeitschrift anorg allge chemie

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Dedicated to Antoine Maignan on the occasion of his 60 th birthday.We present here the syntheses and structural characterizations of inorganic polymeric cluster compounds, Cs[Mn-(salen)] 3 [{Mo 6 Br 6 Se 2 }(CN) 6 ](1) and (H 3 O)(TBA)[Mn-(salen)] 2 [{Mo 6 Br 6 Se 2 }(CN) 6 ] (2) (TBA = tetrabutylammonium ((n-C 4 H 9 ) 4 N + )), built-up from [{Mo 6 Br 6 Se 2 }(CN) 6 ] 4À molecular building blocks and Mn(salen) + complexes (salen = salen = N,N'bis(salicylidene)ethylenediamine). The nature of additional counter cations (i. e. Cs + or TBA + ) enables to control the interactions between the [{Mo 6 Br 6 Se 2 }(CN) 6 ] 4À building blocks and the Mn-(salen) + groups. Thus, 1 was obtained by slow diffusion of a methanol solution of K 2 Cs 2 [{Mo 6 Br 6 Se 2 }(CN) 6 ] cluster compound into a methanol solution of Mn(salen)ClO 4 . 2 was obtained in a similar way but after the addition of tetrabutylammonium bromide into the solution of Mn(salen)ClO 4 . 1 is a bimetallic 3D coordination compound (R � 3c) and 2 is a bimetallic 2D compound (P � 1). Structural correlations between 1 and 2 are discussed and compared with relevant examples found in the literature.

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Synthesis, structure and characterizations of a series of frameworks constructed from octahedral rhenium(III) chalcocyanide clusters, copper(I) and organic units

Ermolaev

¹

,

Mironov

²

2023

Polyhedron

1

0

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Supramolecular Frameworks Based on Rhenium Clusters Using the Synthons Approach

Cited by 5 publications

References 62 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

Playing with [{Mo₆Brⁱ₆Seⁱ₂}(CN)^a₆]⁴⁻ Cluster Building Blocks and Mn(salen)⁺ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

Synthesis, structure and characterizations of a series of frameworks constructed from octahedral rhenium(III) chalcocyanide clusters, copper(I) and organic units

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Supramolecular Frameworks Based on Rhenium Clusters Using the Synthons Approach

Cited by 5 publications

References 62 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

Playing with [{Mo6Bri6Sei2}(CN)a6]4− Cluster Building Blocks and Mn(salen)+ Nodes for the Crystal Engineering of Inorganic Coordination Polymers

Synthesis, structure and characterizations of a series of frameworks constructed from octahedral rhenium(III) chalcocyanide clusters, copper(I) and organic units

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Product

Resources

About

Playing with [{Mo₆Brⁱ₆Seⁱ₂}(CN)^a₆]⁴⁻ Cluster Building Blocks and Mn(salen)⁺ Nodes for the Crystal Engineering of Inorganic Coordination Polymers