Raman Spectroscopic Investigation of Tetraethylammonium Polybromides

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Abstract
A large number of polyhalides, especially polyiodides, have been discovered and studied, but definitive studies on polybromides remain scarce. Br3− is the only monovalent polybromide with a known structure. Higher-order monovalent polybromide anions have been proposed but not structurally confirmed as discrete species. In this study tetraalkylammonium polybromides with molecular formulas R4NBr2x+1 (R = ethyl; x = 1−4) were prepared by reacting tetraalkylammonium monobromide or tribromide salts with gas-phase bromine. Distinct and characteristic Raman spectra were obtained from the solid polybromides in the spectral range between 100 and 400 cm−1. Experimental Raman spectra were compared to ab initio calculations to propose the structure of these polybromide anions. A general agreement between the experimental and theoretical results was observed. This study demonstrates that Raman spectroscopy is a sensitive technique for probing the structure of discrete monovalent polybromides.

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