Heptabismuthate [Bi7I24]3–: a main group element anderson-type structure and its relationships with the polyoxometalates.
We describe the unique structural and electronic arrangement in the heptanuclear polyiodobismuthate [Bi(7)I(24)](3-) which displays striking similarities with the Anderson-type structures found in polyoxometalates. This main group element anion is part of the complex [Bi(OAc)(2)(thf)(4)](3)[Bi(7)I(24)] (1) which has been characterized by X-ray crystallography. We  investigated the structure, stability, and bonding of [Bi(7)I(24)](3-) using relativistic dispersion-corrected density functional theory in combination with a quantitative energy decomposition and electron localization function analysis in order to better understand the main features of this isopolyanion. A comparative analysis of the properties of [Bi(7)I(24)](3-) and previously reported high-nuclearity [Bi(n)X(3n+m)](m-) anions, in the gas phase and in solution, has been performed, in the latter case to track the macroscopic solvent effects. [Bi(7)I(24)](3-) is the largest building block in the class of trianionic iodobismuthates and the sole heptanuclear framework in the family of iodobismuthates.
Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, F-67081 Strasbourg Cedex, France.
Kirill Yu
KY
Monakhov
Christophe
C
Gourlaouen
Roberto
R
Pattacini
Pierre
P
Braunstein