%0 Journal Article %1 noauthororeditor %A Herz, M. A. %A Finzel, K. %A Schnelle, W. %A Ruck, M. %D 2023 %J Z. Anorg. Allg. Chem. %K a %P e202300124 %R 10.1002/zaac.202300124 %T Bismuth-rich intermetallic rods with a note of Zintl-phase %U https://doi.org/10.1002/zaac.202300124 %V 649 %X Black needle-shaped crystals of the bismuth-rich mixed halogenide Bi21Rh4Cl6I7 were obtained by slow cooling of a melt of Bi, RhI3 and BiCl3. Single-crystal X-ray diffraction revealed an orthorhombic structure that consists of infinite intermetallic rods urn:x-wiley:00442313:media:zaac202300124:zaac202300124-math-0001 Bi9Rh23+ and discrete anionic groups BiII2Cl2I53− and BiIIICl4I23−. The rods consist of Rh-centered RhBi8 polyhedra that alternately share triangular and rectangular faces. Using traditional electron counting rules, the rod can be interpreted as a covalent polymer with Rh2 dumbbells bonded to molecular Bi2 and Bi5 units. However, a quantum-chemical bonding analysis shows that the bonds involving Rh atoms are largely diffuse, while two-center bonds dominate in the bismuth units. The below 240 K observed semiconducting behavior of Bi21Rh4Cl6I7 is consistent with a complete localization of the valence electrons. Above 240 K, the resistance along the needle axis is largely independent of temperature.

@article{noauthororeditor, abstract = {Black needle-shaped crystals of the bismuth-rich mixed halogenide Bi21Rh4Cl6I7 were obtained by slow cooling of a melt of Bi, RhI3 and BiCl3. Single-crystal X-ray diffraction revealed an orthorhombic structure that consists of infinite intermetallic rods urn:x-wiley:00442313:media:zaac202300124:zaac202300124-math-0001 Bi9Rh2]3+ and discrete anionic groups [BiII2Cl2I5]3− and [BiIIICl4I2]3−. The rods consist of Rh-centered [RhBi8] polyhedra that alternately share triangular and rectangular faces. Using traditional electron counting rules, the rod can be interpreted as a covalent polymer with Rh2 dumbbells bonded to molecular Bi2 and Bi5 units. However, a quantum-chemical bonding analysis shows that the bonds involving Rh atoms are largely diffuse, while two-center bonds dominate in the bismuth units. The below 240 K observed semiconducting behavior of Bi21Rh4Cl6I7 is consistent with a complete localization of the valence electrons. Above 240 K, the resistance along the needle axis is largely independent of temperature.}, added-at = {2023-10-26T10:58:09.000+0200}, author = {Herz, M. A. and Finzel, K. and Schnelle, W. and Ruck, M.}, biburl = {https://www.bibsonomy.org/bibtex/27672dbfa161da04080fbf88cc484bfb1/ctqmat}, day = 25, description = {Bismuth‐Rich Intermetallic Rods with a Note of Zintl‐Phase - Herz - 2023 - Zeitschrift für anorganische und allgemeine Chemie - Wiley Online Library}, doi = {10.1002/zaac.202300124}, interhash = {5683379c2b18040b11f362dae6826634}, intrahash = {7672dbfa161da04080fbf88cc484bfb1}, journal = {Z. Anorg. Allg. Chem.}, keywords = {a}, month = {07}, pages = {e202300124}, timestamp = {2023-11-23T09:36:11.000+0100}, title = {Bismuth-rich intermetallic rods with a note of Zintl-phase}, url = {https://doi.org/10.1002/zaac.202300124}, volume = { 649}, year = 2023 }