Center for Sustainable Materials Chemistry (CSMC), Oregon State University, USA.
Department of Chemistry, Oregon State University, USA.
Angew Chem Int Ed Engl. 2017 Aug 14;56(34):10140-10144. doi: 10.1002/anie.201701703. Epub 2017 Jun 14.
Dodecameric (Sn ) and hexameric topologies dominate monoalkyltin-oxo cluster chemistry. Their condensation, triggered by radiation exposure, recently produced unprecedented patterning performance in EUV lithography. A new cluster topology was crystallized from industrial n-BuSnOOH, and additional characterization techniques indicate other clusters are present. Single-crystal X-ray analysis reveals a β-Keggin cluster, which is known but less common than other Keggin isomers in polyoxometalate and polyoxocation chemistry. The structure is formulated [NaO (BuSn) (OH) (O) (OCH ) (Sn(H O) )] (β-NaSn ). SAXS, NMR, and ESI MS differentiate β-NaSn , Sn , and other clusters present in crude "n-BuSnOOH" and highlight the role of Na as a template for alkyltin Keggin clusters. Unlike other alkyltin clusters that are cationic, β-NaSn is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.
十二聚体（Sn）和六聚体拓扑结构主导单烷基金属锡-氧簇化学。它们的缩合反应，由辐射引发，最近在极紫外光刻中产生了前所未有的图案化性能。一种新的簇拓扑结构从工业 n-BuSnOOH 中结晶出来，并且其他的特征技术表明还存在其他的簇。单晶 X 射线分析揭示了一个 β-Keggin 簇，它在多金属氧酸盐和多氧阳离子化学中是已知的，但比其他 Keggin 异构体更为常见。该结构被表述为[NaO（BuSn）（OH）（O）（OCH ）（Sn（H O））]（β-NaSn）。小角 X 射线散射（SAXS）、核磁共振（NMR）和电喷雾质谱（ESI MS）区分了β-NaSn、Sn 和其他存在于粗制“n-BuSnOOH”中的簇，并强调了 Na 作为烷基金属锡 Keggin 簇模板的作用。与其他带正电荷的烷基锡簇不同，β-NaSn 是中性的。因此，它作为一个独特的模型体系，不存在抗衡离子，用于研究簇到薄膜和纳米图案的转化。
