On iodido bismuthates, bismuth complexes and polyiodides with bismuth in the system BiI3/18-crown-6/I2
Author:
Notter Silke1, Donsbach Carsten1, Feldmann Claus1
Affiliation:
1. Institute for Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) , Engesserstraße 15 , D-76131 Karlsruhe , Germany
Abstract
Abstract
The iodido bismuthates [Bi(18-crown-6)I2][BiI4] (1) and [Bi(18-crown-6)I2][Bi3I10] (2), the neutral complex [Bi(C6H14O4)I3](18-crown-6) (3) as well as the polyiodides [Bi(18-crown-6)I2][I5](18-crown-6) (4), [Bi(18-crown-6)I2]2[I14] (5) and [Bi(18-crown-6)I2]2[I19] (6) were prepared by reaction of BiI3, 18-crown-6, and I2 at T = 60–120 °C. The compounds 1–5 were prepared in [n-Bu3MeN][N(Tf)2] as an ionic liquid ([n-Bu3MeN]: tributylmethylammonium, [N(Tf)2]: bis(trifluoromethylsulfonyl)imide), whereas 6 was obtained only by direct reaction of the starting materials. The title compounds exhibit two different constitutions of the [Bi(18-crown-6)I2]+ cation as well as a non-charged, molecular [Bi(C6H14O4)I3] unit with a triethylene glycol ligand generated in situ by cleavage of the crown ether. Infinite chain-like
[
BiI
2
/
1
I
4
/
2
]
−
∞
1
${}_{\infty }{}^{1}\left[{{\text{BiI}}_{2/1}{\text{I}}_{4/2}\right]}^{-}$
and
[
Bi
6
I
18
/
1
I
4
/
2
∞
1
]
−
${{}_{\infty }{}^{1}\left[{\text{Bi}}_{6}{\text{I}}_{18/1}{\text{I}}_{4/2}\right]}^{-}$
anions occur in 1 and 2, whereas various polyiodide anions (e.g. [I3]−, [I5]−, [I7]−, [I9]−) with partly complex interaction are observed in 4, 5, and 6. The title compounds were characterized by single-crystal X-ray diffraction analysis and infrared spectroscopy. In the case of 1 and 2, the optical band gap was determined to be E
g
= 1.91 and 1.62 eV, respectively. Especially, the ionic-liquid-based synthesis affords the different metastable compounds with variable composition and structure in a narrow temperature range.
Publisher
Walter de Gruyter GmbH
Subject
General Chemistry
Reference38 articles.
1. Pedersen, C. J. Am. Chem. Soc. 1967, 89, 7017–7036. https://doi.org/10.1021/ja01002a035. 2. Bradshaw, J. S., Izatt, R. M. A., Bordunov, V., Zhu, C. Y., Hathaway, J. K. Crown ethers. In Gokel, G. W., Ed.; Compr. Supramol. Chem., Vol. 1, 1996; Elsevier Science: Oxford; pp. 35–96. chapter 2. 3. Liu, Z., Nalluri, S. K. M., Stoddart, J. F. Chem. Soc. Rev. 2017, 46, 2459–2478. https://doi.org/10.1039/c7cs00185a. 4. Gokel, G. W., Leevy, W. M., Weber, M. E. Chem. Rev. 2004, 104, 2723–2750. https://doi.org/10.1021/cr020080k. 5. Nelson, J., Mckee, V., Morgan, G. Progr. Inorg. Chem. 1997, 47, 167–316.
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