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. 2020 Dec 8;25(24):5796.
doi: 10.3390/molecules25245796.

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

Aleksei S Pronin  1 , Spartak S Yarovoy  1 , Yakov M Gayfulin  1 , Aleksey A Ryadun  1 , Konstantin A Brylev  1 , Denis G Samsonenko  1 , Ilia V Eltsov  2 , Yuri V Mironov  1
Affiliations

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

Aleksei S Pronin et al. Molecules. .

Abstract

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.

Keywords: cluster compounds; crystal structure; cyanide ligand; hydrolytic stability; luminescence; molybdenum; tungsten.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
The synthetic ways of obtaining the compounds 1–5.
Figure 1
Figure 1
Experimental (top) vs calculated (bottom) powder diffraction patterns for compounds 4 (a) and 5 (b).
Figure 2
Figure 2
Experimental 13C-NMR spectra for compounds 4 (a) and 5 (b) in DMSO-d6 solution.
Figure 3
Figure 3
UV-Vis spectra of compounds 4 (a) and 5 (b) recorded for the freshly prepared aqueous solutions and for the solutions aged for 1 month.
Figure 4
Figure 4
Structure of the [{Mo6I8}(CN)6]2− cluster anion in the structure of compound 2. Atoms are shown as thermal ellipsoids of 50% probability (a); packing of the cluster anions and Bu4N+ cations in the structure of compound 2, view in bc plane (b).
Figure 5
Figure 5
Structure of the [{Mo6I8}(CN)4(MeO)2]2− cluster anions in the structure of compound 4 (a); structure of the [{W6I8}(CN)2(MeO)4]2− cluster anion in the structure of compound 5 (b); atoms are shown as thermal ellipsoids of 50% probability.
Figure 6
Figure 6
Left: energy level diagrams of the [{Mo6I8}(CN)6]2−, trans-[{Mo6I8}(CN)4(MeO)2]2−, and trans-[{W6I8}(CN)2(MeO)4]2− cluster anions (a–c, respectively). Right: structure of the HOMOs and LUMOs of the [{Mo6I8}(CN)6]2−, trans-[{Mo6I8}(CN)4(MeO)2]2−, and trans-[{W6I8}(CN)2(MeO)4]2− cluster anions (a–c, respectively).
Figure 7
Figure 7
Normalized emission spectra of compounds 2, 4 and 5 in acetonitrile solutions.
See this image and copyright information in PMC

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