Sensitivity of Mild Hydrothermal Synthesis to the Reaction Conditions: Targeting Mixed-Metal Hexagonal Tungsten Bronze Fluorides A x M 2+ x M 3+ (1–x) F 3 to Investigate Their Magnetic Behavior

Masachchi, Lakshani W; Keerthisinghe, Navindra; Berseneva, Anna A; Morrison, Gregory; Smith, Mark D; Breton, Logan S; Schorne-Pinto, Juliano; Aziziha, Mina; zur_Loye, Hans-Conrad

doi:10.1021/acs.inorgchem.4c02307

The possibility that MX 3 − anions can interact with one another is assessed via ab initio calculations in gas phase as well as in aqueous and ethanol solution. A pair of such anions can engage in two different dimer types. In the bridged configuration, two X atoms engage with two M atoms in a rhomboid structure with four equal M–X bond lengths. The two monomers retain their identity in the stacked geometry which contains a pair of noncovalent M⋯X interactions. The relative stabilities of these two structures depend on the nature of the central M atom, the halogen substituent, and the presence of solvent. The interaction and binding energies are fairly small, generally no more than 10 kcal mol −1 . The large electrostatic repulsion is balanced by a strong attractive polarization energy.

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