Date Thesis Awarded

4-2021

Access Type

Honors Thesis -- Access Restricted On-Campus Only

Degree Name

Bachelors of Science (BS)

Department

Chemistry

Advisor

Robert Pike

Committee Members

Randolph Coleman

Robert Barnet

William McNamara

Abstract

The reaction of bismuth(III) iodide (BiI3) and alkylpyridinium iodides (RPyI, R= Me, Et, Pr, Bu) in either MeCN or Me2CO solvents yields crystal products when layered with ethyl ether, or cooled to −5 oC for multiple days. The alkylpyridinium iodobismuthates show a variety of stoichiometric compound and with corresponding unique structures, ranging from the 1-D chain structure {(MePy)[BiI4]}n to the discrete cluster structure in (EtPy)4[Bi6I22]•2MeCN. A diverse range of iodobismuthate anion clusters ranging from [Bi2I9]3− to [Bi6I22]4− were identified in the ten novel alkylpyridinium iodobismuthate crystal structures created. Increasing the size of the pyridinium cation alkyl chain appears to correlate with an increased preference towards formation of larger anion clusters. Powder X-ray diffraction was conducted on bulk products from synthesis with each different alkyl R group (Me-Bu) the results showed {(MePy)[BiI4]}n, (EtPy)3[Bi3I12], (PrPy)4[Bi4I16], and (BuPy)4[Bi4I16] to be the most prevalent phases in the bulk products. Thermogravimetric analysis was conducted on bulk products and showed each complex to be stable up until 300 oC. Various crystal structures were found when using different solvents (MeCN or Me2CO) and when preforming different crystallization techniques. All structures identified were revealed through single crystal X-ray diffraction.

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