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Hausmann D, Feldmann C. Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2. Inorg Chem. 2016;55(12):6141-7doi: 10.1021/acs.inorgchem.6b00663.
Hausmann, D., & Feldmann, C. (2016). Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2. Inorganic chemistry, 55(12), 6141-7. https://doi.org/10.1021/acs.inorgchem.6b00663
Hausmann, David, and Feldmann, Claus. "Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2." Inorganic chemistry vol. 55,12 (2016): 6141-7. doi: https://doi.org/10.1021/acs.inorgchem.6b00663
Hausmann D, Feldmann C. Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2. Inorg Chem. 2016 Jun 20;55(12):6141-7. doi: 10.1021/acs.inorgchem.6b00663. Epub 2016 Jun 09. PMID: 27281122.
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Inorg Chem. 2016 Jun 20;55(12):6141-7. doi: 10.1021/acs.inorgchem.6b00663. Epub 2016 Jun 09.

Bromine-rich Zinc Bromides: Zn6Br12(18-crown-6)2×(Br2)5, Zn4Br8(18-crown-6)2×(Br2)3, and Zn6Br12(18-crown-6)2×(Br2)2.

Inorganic chemistry

David Hausmann, Claus Feldmann

Affiliations

  1. Institut für Anorganische Chemie, Karlsruhe Institute of Technology (KIT) Engesserstrasse 15, D-76131 Karlsruhe, Germany.

PMID: 27281122 DOI: 10.1021/acs.inorgchem.6b00663

Abstract

The bromine-rich zinc bromides Zn6Br12(18-crown-6)2×(Br2)5 (1), Zn4Br8(18-crown-6)2×(Br2)3 (2), and Zn6Br12(18-crown-6)2×(Br2)2 (3) are prepared by reaction of ZnBr2, 18-crown-6, and elemental bromine in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2 = bis(trifluoromethylsulfonyl)amide). Zn6Br12(18-crown-6)2×(Br2)5 (1) is formed instantaneously by the reaction. Even at room temperature, compound 1 releases bromine, which was confirmed by thermogravimetry (TG) and mass spectrometry (MS). The release of Br2 can also be directly followed by the color and density of the title compounds. With controlled conditions (2 weeks, 25 °C, absence of excess Br2) Zn6Br12(18-crown-6)2×(Br2)5 (1) slowly releases bromine with conconcurrent generation of Zn4Br8(18-crown-6)2×(Br2)3 (2) (in ionic liquid) and Zn6Br12(18-crown-6)2×(Br2)2 (3) (in inert oil). All bromine-rich zinc bromides contain voluminous uncharged (e.g., Zn3Br6(18-crown-6), Zn2Br4(18-crown-6)) or ionic (e.g., [Zn2Br3(18-crown-6)](+), [(Zn2Br6)×(Br2)2](2-)) building units with dibromine molecules between the Zn oligomers and partially interconnecting the Zn-containing building units. Due to the structural similarity, the bromine release is possible via crystal-to-crystal transformation with retention of the crystal shape.

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