Heptabismuthate [Bi7I24]3–: a main group element anderson-type structure and its relationships with the
Kirill Yu Monakhov1, Christophe Gourlaouen, Roberto Pattacini
1Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, F-67081 Strasbourg Cedex, France.
Abstract:
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.
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