Next Article in Journal
The Detection of Monoclinic Zirconia and Non-Uniform 3D Crystallographic Strain in a Re-Oxidized Ni-YSZ Solid Oxide Fuel Cell Anode
Previous Article in Journal
Characterization of Pure Face-Shear Strain in Piezoelectric α-Tellurium Dioxide (α-TeO2)
Previous Article in Special Issue
Revealing the Bonding Nature in an ALnZnTe3-Type Alkaline-Metal (A) Lanthanide (Ln) Zinc Telluride by Means of Experimental and Quantum-Chemical Techniques
Open AccessArticle

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

1
Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1-3, 119991 Moscow, Russia
2
Kurnakov Institute of General and Inorganic Chemistry of RAS, Leninskii pr. 31, 119991 Moscow, Russia
*
Author to whom correspondence should be addressed.
Crystals 2020, 10(10), 940; https://doi.org/10.3390/cryst10100940
Received: 17 September 2020 / Revised: 8 October 2020 / Accepted: 15 October 2020 / Published: 16 October 2020
(This article belongs to the Special Issue Intermetallic)
A bismuth subbromide, Bi6Br7, was synthesized in the form of single crystals using the reaction between Bi and Hg2Br2 in a gradient furnace. Its crystal structure was reinvestigated by low-temperature single-crystal X-ray diffraction (Pnnm, a = 15.4996(6) Å, b = 23.6435(7) Å, c = 9.0231(2) Å, Z = 8, R1 = 0.041, wRall = 0.087). Based on the diffraction data, the structure description was revised as containing Bi95+ cluster polycations and 1[Bi3Br145−] ladder-like anions. DFT calculations of band structure showed the compound to be a narrow-gap semiconductor with a band gap of ca. 1.3 eV, with the nature of the compound as ionic salt confirmed by charge density analysis. Direct-space bonding analysis based on the ELF topology and QTAIM partitioning, performed for all known homoatomic bismuth polycations, as well as isoelectronic main-group metal ions, shows patterns of localized pairwise and three-center bonding forming the frameworks of the clusters. In addition to obtaining new data, the use of highly augmented basis sets allowed us to revise and amend several previously made conclusions regarding bonding in such species. View Full-Text
Keywords: metal-metal bonds; main-group clusters; bismuth polycations; subvalent halides; crystal structure; DFT calculations; band structure; ELF metal-metal bonds; main-group clusters; bismuth polycations; subvalent halides; crystal structure; DFT calculations; band structure; ELF
Show Figures

Graphical abstract

MDPI and ACS Style

Stroganova, E.A.; Troyanov, S.I.; Morozov, I.V.; Kuznetsov, A.N. Bismuth Polycations Revisited: Alternative Synthesis and Electronic Structure of Bi6Br7, and Bonding in Main-Group Polyatomic Ions from a Direct Space Perspective. Crystals 2020, 10, 940.

Show more citation formats Show less citations formats
Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Article Access Map by Country/Region

1
Search more from Scilit
 
Search
Back to TopTop