Organo-oxo tin clusters have been researched for a variety of applications and have found use as organic-inorganic hybrids for surface coatings, catalysis, anti-fungal agents, and polymer additives. More recently, clusters of the type [(BuSn)12O14(OH)6]X2 and [BuSnOO2R]6 have been investigated as thin film inorganic resist materials for extreme ultraviolet (EUV) lithography. Both of the above clusters are synthesized through condensation of a mono-alkyl stannonic acid with a second acid, and derivatives based on carboxylic and phosphorus-based acids are well known in the literature. However, the reactivity of the clusters themselves have not yet been extensively explored. In this work, the reactivity of these species is investigated using a variety of azoles and similar compounds to deduce the effects of acidity and basicity on the formation and degradation of the clusters. Three sets of experiments examine the mechanisms of formation of the clusters from butyltin stannonic acid, the degradation of [BuSnOO2CH3]6, and perhaps most interesting, mechanisms of conversion that exist between [BuSnOO2R]6 and [(BuSn)12O14(OH)6]X2. Each reaction was observed with 1H, 119Sn, and 1H DOSY NMR to track the formation, disappearance, or interconversion of the clusters, while stable reaction intermediates and products were additionally analyzed with XPS and X-ray crystallography. The intricate picture of cluster reactivity that this work provides suggests that these clusters are susceptible to a wider range of reactivity than the literature currently depicts, which will have definite impacts on current and future applications of these materials.

Organo-oxo tin cluster reactivity: Insight into cluster formation, degradation, and interconversion

253rd National Meeting (2017)

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