%0 Journal Article %1 groh_pentagonal_2017 %A Groh, Matthias F. %A Wolff, Alexander %A Wahl, Bernhard %A Rasche, Bertold %A Gebauer, Paul %A Ruck, Michael %D 2017 %J Z. Anorg. Allg. Chem. %K %N 1 %P 69--80 %R 10.1002/zaac.201600354 %T Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by Low-Temperature Syntheses %U http://onlinelibrary.wiley.com/doi/10.1002/zaac.201600354/abstract %V 643 %X We present the syntheses, crystal structures, and properties of five metal-rich salts containing the Bi104+ pentagonal antiprism with an endohedral palladium or, for the first time, platinum atom. Tetragonal Pt@Bi10(AlBr4)4 P42/n at 296(1) K; P4 at 150(2) K was obtained by reacting platinum, bismuth, and bismuth tribromide in BMImBr·4.1AlBr3 at 140 °C (BMIm = 1-butyl-3-methylimidazolium). Monoclinic Pt@Bi10(AlBr4)2(Al2Br7)2 P21/n occurs as by-product. The two corresponding palladium compounds result from the dissolution of Bi16PdCl22 in BMImBr·4.1AlBr3. Pd@Bi10(AlBr4)4 P42/n adopts a disordered structure homeotypic to its platinum analog. Pd@Bi10(AlBr4)2(Al2Br7)2 P21/n is isostructural to Pt@Bi10(AlBr4)2(Al2Br7)2. In all structures, the M@Bi104+ cations are well separated by the bromido-aluminate anions with inter-cluster Bi···Bi distances longer than 520 pm. This is not the case in Pd@Bi10Bi2Sn6Cl22, which crystallized from a tin-containing melt of the metals and BiCl3. In its monoclinic structure P21/c, the cluster cations are arranged in chains along 001 with an inter-cluster distance of only 357 pm. Despite further structural evidence, DFT-based quantum chemical analysis gave no hint on inter-cluster bonding. According to the calculated band structure as well as resistivity and magnetic susceptibility measurements, the black compound is a diamagnetic semiconductor.

@article{groh_pentagonal_2017, abstract = {We present the syntheses, crystal structures, and properties of five metal-rich salts containing the Bi104+ pentagonal antiprism with an endohedral palladium or, for the first time, platinum atom. Tetragonal [Pt@Bi10](AlBr4)4 [P42/n at 296(1) K; P4 at 150(2) K] was obtained by reacting platinum, bismuth, and bismuth tribromide in [BMIm]Br·4.1AlBr3 at 140 °C (BMIm = 1-butyl-3-methylimidazolium). Monoclinic [Pt@Bi10](AlBr4)2(Al2Br7)2 [P21/n] occurs as by-product. The two corresponding palladium compounds result from the dissolution of Bi16PdCl22 in [BMIm]Br·4.1AlBr3. [Pd@Bi10](AlBr4)4 [P42/n] adopts a disordered structure homeotypic to its platinum analog. [Pd@Bi10](AlBr4)2(Al2Br7)2 [P21/n] is isostructural to [Pt@Bi10](AlBr4)2(Al2Br7)2. In all structures, the [M@Bi10]4+ cations are well separated by the bromido-aluminate anions with inter-cluster Bi···Bi distances longer than 520 pm. This is not the case in [Pd@Bi10][Bi2Sn6Cl22], which crystallized from a tin-containing melt of the metals and BiCl3. In its monoclinic structure [P21/c], the cluster cations are arranged in chains along [001] with an inter-cluster distance of only 357 pm. Despite further structural evidence, DFT-based quantum chemical analysis gave no hint on inter-cluster bonding. According to the calculated band structure as well as resistivity and magnetic susceptibility measurements, the black compound is a diamagnetic semiconductor.}, added-at = {2024-03-25T12:50:48.000+0100}, author = {Groh, Matthias F. and Wolff, Alexander and Wahl, Bernhard and Rasche, Bertold and Gebauer, Paul and Ruck, Michael}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/21a497f4d7d22c18a4606f2e6f60e5478/brasche}, doi = {10.1002/zaac.201600354}, file = {Groh et al_2017_Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by.pdf:files/2733/Groh et al_2017_Pentagonal Bismuth Antiprisms with Endohedral Palladium or Platinum Atoms by.pdf:application/pdf}, interhash = {c2de014e7dd7e0f487962576bf1ba07f}, intrahash = {1a497f4d7d22c18a4606f2e6f60e5478}, issn = {1521-3749}, journal = {Z. Anorg. Allg. Chem.}, keywords = {}, language = {en}, month = {01}, number = 1, pages = {69--80}, timestamp = {2024-03-25T11:50:48.000+0100}, title = {Pentagonal {Bismuth} {Antiprisms} with {Endohedral} {Palladium} or {Platinum} {Atoms} by {Low}-{Temperature} {Syntheses}}, url = {http://onlinelibrary.wiley.com/doi/10.1002/zaac.201600354/abstract}, urldate = {2017-04-10}, volume = 643, year = 2017 }