Low dimensional solids based on Mo6cluster cyanides and Mn2+, Mn3+or Cd2+metal ions: crystal chemistry, magnetic and optical properties

Daigre, Gilles; Lemoine, Pierric; Pham, Thi Diep; Demange, Valérie; Gautier, Régis; Наумов, Н. Г.; Ledneva, A. Yu.; Amela-Cortés, Maria; Dumait, Noée; Audebrand, Nathalie; Cordier, Stéphane

doi:10.1039/c8ce00113h

Cited by 8 publications

(5 citation statements)

References 77 publications

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“…Each Mo atom of the cluster core is coordinated by apical CN − ligand. The Mo-C distances display the average length of 2.188(8) Å, which is in the range of values that were reported for hexanuclear cyanide clusters of Mo [ 32 , 43 , 44 ]. The crystal packing includes the cluster anions forming a column along the a axis and Bu 4 N + cations, which fill the space between anions forming a cationic sublattice with channel cavities ( Figure 4 b).…”

Section: Resultssupporting

confidence: 68%

“…Until now, only one structure of a cyanide cluster based on halide octahedral molybdenum core has been reported, namely [Mo 6 Br 8 (CN) 6 ] 2− [ 31 ]. It was shown that this complex formed polymeric compounds with transition metal cations [ 32 ]. For octahedral tungsten halides, cyanide compounds have not been described.…”

Section: Resultsmentioning

confidence: 99%

“…Using {M 6 X 8 }-type cyanoclusters is interesting for obtaining new luminescent coordination polymers. For now, the structure of only one cyanide cluster based on an {Mo 6 X 8 } 4+ core has been described in the literature, namely [{Mo 6 Br 8 }(CN) 6 ] 2− [ 31 , 32 ], while the tungsten cyanide clusters of that type are unknown. Therefore, further progress in this field requires the development of methods for the synthesis of cyanide molybdenum and tungsten halide clusters.…”

Section: Introductionmentioning

confidence: 99%

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Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

et al. 2020

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Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2–, trans-[{Mo6I8}(CN)4(MeO)2]2– and trans-[{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands.

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Section: Resultssupporting

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

et al. 2020

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“…1d) with cyanide ligands (O1…N2 = 3.33(1)Å, symmetry code for N2: 1-x, -y, 1-z). As calculated by the program PLATON, [12] the effective free volume in 1 is 88.5 Å 3 corresponding to 6.5% of the crystal volume. When crystals of 1 are heated at 180 °C for 30 min, the solvent (MeOH) is removed to form (1') which has the same layered framework as (1).…”

Section: Resultsmentioning

confidence: 99%

“…When the terminal ligands are equipped with suitable ditopic ligands, the clusters can be used as building blocks together with simple metal ions or coordinatively unsaturated complexes for the preparation of supramolecular assemblies or polymeric architecture. [11][12] For example, our group has focused on using edge-caped octahedral [Nb 6 Cl 12 (CN) 6 ] 4− cluster and transition metal complexes as building blocks. 13 Most reported cluster-containing molecular assemblies are based on {Re 6 }, {W 6 }, {Mo 6 }, {Zr 6 } and {Nb 6 } cluster units.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Complexes Built of Octahedral [Ta6Cl12(CN)6]3−/4− Clusters and Terpyridine-Metal Complexes

2022

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The preparation and characterization of two supramolecular complexes from octahedral [Ta 6 Cl 12 (CN) 6 ] 4-/3units and 2, 2': 6', 2''-terpyridine (Terpy) metal complexes as building blocks are reported. Single crystal analyses revealed [Mn(Terpy)] 2 [Ta 6 Cl 12 (CN) 6 ]•MeOH (1) features a neutral twodimensional (2D) framework composed of layers based on [Ta 6 Cl 12 (CN) 6 ] 4and [Mn(Terpy)] 2+ . Each layer is built of 6-connected [Ta 6 Cl 12 ] 2+ and 3-connected Mn(II) nodes bridged by cyanide ligands. The layers are held together by MeOH molecules. The layered structure is maintained after the removal of solvent molecule (MeOH) upon heating, leading to the formation of [Mn(Terpy] 2 [Ta 6 Cl 12 (CN) 6 ] (1'). In the case of using Gd 3+ , the resultant product was revealed by single-crystal analyses to be an ionic 2). 2 has a three-dimensional (3D) framework built of [Gd(Terpy)(H 2 O) 4 (DMF) 2 ] 3+ and [Ta 6 Cl 12 (CN) 6 ] 3ions connected to each other via extensive hydrogen bonds and p-p interactions between the cations, anions, and solvent molecules. Thermal stabilities of 1-2 are reported.

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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

Daigre

Tarasenko

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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Low dimensional solids based on Mo₆cluster cyanides and Mn²⁺, Mn³⁺or Cd²⁺metal ions: crystal chemistry, magnetic and optical properties

Abstract: Five new cluster compounds based on [Mo6Bri8(CN)a6]2− and [Mo6Bri6Qi2(CN)a6]n− (Q = S, Se, n = 3, 4) cluster units have been synthesized and characterized.

Cited by 8 publications

References 77 publications

Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Supramolecular Complexes Built of Octahedral [Ta6Cl12(CN)6]3−/4− Clusters and Terpyridine-Metal Complexes

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

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Low dimensional solids based on Mo6cluster cyanides and Mn2+, Mn3+or Cd2+metal ions: crystal chemistry, magnetic and optical properties

Abstract: Five new cluster compounds based on [Mo6Bri8(CN)a6]2− and [Mo6Bri6Qi2(CN)a6]n− (Q = S, Se, n = 3, 4) cluster units have been synthesized and characterized.

Cited by 8 publications

References 77 publications

Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Cyanide Complexes Based on {Mo6I8}4+ and {W6I8}4+ Cluster Cores

Supramolecular Complexes Built of Octahedral [Ta6Cl12(CN)6]3−/4− Clusters and Terpyridine-Metal Complexes

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

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Low dimensional solids based on Mo₆cluster cyanides and Mn²⁺, Mn³⁺or Cd²⁺metal ions: crystal chemistry, magnetic and optical properties

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