Low-Temperature Ordering in the Cluster Compound (Bi8)Tl[AlCl4]3

Abstract

The reaction of Bi, BiCl3, and TlCl in the ionic liquid [BMIm]Cl·4AlCl3 (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive black crystals of (Bi8)Tl[AlCl4]3. X-ray diffraction on single crystals at room temperature revealed a structure containing [ Tl ( AlCl 4 ) 3 ] ∞ 1 2 − strands separated by isolated Bi82+ square antiprisms. The thallium(I) ion is coordinated by twelve Cl− ions of six [AlCl4]− groups, resulting in a chain of face-sharing [TlCl12]11− icosahedra. The Bi82+ polycation is disordered, simulating a threefold axis through its center and overall hexagonal symmetry (space group P63/m). Slowly cooling the crystals to 170 K resulted in increased order in the Bi8 cluster orientations. An ordered structure model in a supercell with a’ = 2a, b’ = 2b, c’ = 3c and the space group P65 was refined. The structure resembles a hexagonal perovskite, with complex groups in place of simple ions.

Hexacyanidosilicates with Functionalized Imidazolium Counterions

“…By combining cations and anions in a wide variety of ways, or by selectively modifying organic groups of the ions, physical properties such as melting point, viscosity, high thermal stability, volatility and acidity can be influenced, which is why ILs are also called “designer solvents” . Due to these variable properties, ILs have been extensively investigated in recent years and have been used, for example, as solvents in organic and catalytic syntheses, as electrolyte liquids in batteries, as additives in dye cells, as extraction media for metals or for the synthesis of nanoparticles, and metal clusters . Furthermore, they are used in processes such as dissolving of cellulose or for the synthesis of alkoxyphenyl‐phosphines in the industrial BASIL™ process ,…”

Bismuth Polycations Revisited: Alternative Synthesis and Electronic Structure of Bi6Br7, and Bonding in Main-Group Polyatomic Ions from a Direct Space Perspective

“…In the next six decades, other binary and ternary compounds featuring this cation followed [3][4][5][6][7][8][9][10][11][12][13]. A number of other species were also discovered, such as 'classical' Bi 5 3+ [14][15][16][17][18][19] and Bi 8 2+ [13,14,[20][21][22][23][24], and more recent additions Bi 5 + [25,26], Bi 6 2+ [26,27], and Bi 10 4+ , although the latter has not been obtained as a true homoatomic unity and was mostly centered by palladium or platinum, or on rare occasion even by gold [28][29][30][31] (we leave its capped forms outside the scope of this paper as their homoatomic nature is questionable, as well as other heteroatomic bismuth clusters). The compounds that contain these polycations are essentially complex salts, with counterions for bismuth clusters being metal halide anions.…”

“…The compounds that feature bismuth cluster polycations turned out to be rather difficult to work with, due to them often being air-and moisture-sensitive, and particularly complex objects for the X-ray crystallography, for both technical and fundamental reasons (e.g., a tendency to show pseudo-symmetry or form disordered arrangements) [22,24]. As a consequence, some of the reported structures, particularly those from earlier times, were plagued by errors.…”

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

“…Besides application in classic solid state chemistry, ILs can be used as reaction media to prepare (oligomeric) metal complexes, metal organic frameworks, coordination polymers [25–35] or cluster compounds incorporating main group elements [36–41] . Within SPP 1708, the synthesis of intermetallic cluster and nanoparticles, [3,42–56] the controlled synthesis of polyanions and cations, [57–61] solvent‐free chalcogenidometal‐containing materials, [62–75] deposition of nanocrystalline materials, [76–80] ionic liquids as precursors for inorganic materials, [81–83] ionic‐liquid‐modified hybrid materials, [84–87] as well as the low‐temperature synthesis of thermoelectric materials [88–92] were investigated. Moreover, theoretical [93–106] and solubility [107–114] aspects during the synthesis process were studied.…”

“…[12][13][14][15][16][17][18][19][20][21][22][23][24] Besides application in classic solid state chemistry, ILs can be used as reaction media to prepare (oligomeric) metal complexes, metal organic frameworks, coordination polymers [25][26][27][28][29][30][31][32][33][34][35] or cluster compounds incorporating main group elements. [36][37][38][39][40][41] Within SPP 1708, the synthesis of intermetallic cluster and nanoparticles, [3,[42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] the controlled synthesis of polyanions and cations, [57][58][59]…”