Volatile β-diketonate complexes of Rb-Co: effect of incorporation a neutral ligand 18-crown-6 ether

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Abstract

Heterometallic β-diketonate complexes MI[M(L)n] containing alkali metal cations MI are of great interest from the point of view of their use in the preparation of halide perovskites. However, such compounds are poorly studied for MI = Rb and there is no information on their crystal structure. In this work, two types of such complexes are presented: Rb[Co(hfac)3] 1 and novel [Rb(18C6)][Co(hfac)3] 2 (hfac = CF3COCHCOCF3–, hexafluoroacetylacetonate ion, 18C6 = 18-crown-6 ester). The compounds were characterized by elemental analysis, IR spectroscopy, single-crystal and powder XRD, and TGA. Both complexes have a chain polymeric structure, whereas the inclusion of the neutral 18C6-ligand effectively reduces the number of contacts between the cation and the complex anion [Co(hfac)3]–. Both heterometallic complexes are more thermally stable than Rb(hfac), with 1 partially transitioning into the gas phase at atmospheric pressure.

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D. V. Kochelakov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences

Author for correspondence.
Email: pi-3@outlook.com
Russian Federation, Novosibirsk, 630090

P. S. Stabnikov

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences

Email: pi-3@outlook.com
Russian Federation, Novosibirsk, 630090

E. S. Vikulova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences

Email: pi-3@outlook.com
Russian Federation, Novosibirsk, 630090

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Supplementary files

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2. Fig. 1. Diffraction patterns of synthesis products 1 and 2.

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3. Fig. 2. Fragment of the Rb[Co(hfac)3] chain (a), chains in the (110) direction (b).

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4. Fig. 3. Hexagonal motif of packing of Rb[Co(hfac)3] chains.

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5. Fig. 4. Fragment of the [Rb(18C6)][Co(hfac)3] chain (a), chains along the a direction are shown without positional disorder for clarity (b).

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6. Fig. 5. Hexagonal motif of [Rb(18C6)][Co(hfac)3] (perpendicular to the a axis).

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7. Fig. 6. Thermograms of Rb(hfac), [Co(H2O)2(hfac)2], Rb[Co(hfac)3] and [Rb(18C6)][Co(hfac)3] (He atmosphere, heating rate 10 deg/min).

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