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The Role of [BF 4 ] − and [B(CN) 4 ] − Anions in the Ionothermal Synthesis of Chalcogenidometalates
Author(s) -
Santner Silke,
Sprenger Jan A. P.,
Finze Maik,
Dehnen Stefanie
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705297
Subject(s) - ionic liquid , chemistry , ion , crystallography , crystal structure , boron , absorption (acoustics) , ionic bonding , inorganic chemistry , materials science , catalysis , organic chemistry , composite material
The role of borate anions in ionothermal syntheses of crystalline chalcogenidometalates was shown by the directed ionothermal synthesis of seven new selenidostannates in ionic liquids with either [BF 4 ] − or [B(CN) 4 ] − anions. Single crystal structures are presented of four compounds, (C 4 C 1 C 1 Im) 5 [Sn 9 Se 20 ][BF 4 ] ( 1 , Im=imidazolium), (DMMPH) 4 [Sn 2 Se 6 ] ( 2 , DMMP=2,6‐dimethylmorpholine), (C 2 C 1 Im) 2 (DMMPH) 2 [Sn 6 Se 14 ] ( 3 ), and K 2 [Sn 3 Se 7 ] ( 4 ), and how the chosen ionic liquid anion, and the reaction temperature, influences the product spectrum is discussed: Notably, 1 contains an entire formula unit of the ionic liquid, (C 4 C 1 C 1 Im)[BF 4 ], while 4 contains neither the cation nor the anion of the ionic liquid—both observations being very uncommon for ionothermal syntheses. Three further compounds were obtained that exhibit strong disorder in the crystal structures ( I ‐ III ), for which only their anionic substructures are discussed herein. Compound 4 and I‐III are based on the same layered selenidostannate substructure, 2D‐{[Sn 3 Se 7 ] 2− }, yet with different inter‐layer distances, which is clearly reflected in the crystal colors and quantitative optical absorption properties.