Alkyltin Keggin Clusters Templated by Sodium. Issue 34 (14th June 2017)

• Record Type: Journal Article
• Authors: Saha, Sumit; Park, Deok‐Hie; Hutchison, Danielle C.; Olsen, Morgan R.; Zakharov, Lev N.; Marsh, David; Goberna‐Ferrón, Sara; Frederick, Ryan T.; Diulus, J. Trey; Kenane, Nizan; Herman, Gregory S.; Johnson, Darren W.; Keszler, Douglas A.; Nyman, May
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 34(2017)
• Page Start: 10140
• Page End: 10144
• Publication Date: 2017-06-14
• Subjects: alkyltin clusters -- Keggin clusters -- nanopatterning -- small-angle X-ray scattering; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201701703
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Dodecameric (Sn12 ) 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 [NaO4 (BuSn)12 (OH)3 (O)9 (OCH3 )12 (Sn(H2 O)2 )] (β‐NaSn13 ). SAXS, NMR, and ESI MS differentiate β‐NaSn13, Sn12, 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‐NaSn13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns. Abstract : Fishing for facts : Solution‐phase characterization of n ‐BuSnOOH and structure determination of a neutral sodium‐centered organotin Keggin cluster (β‐NaSn13 ) extracted from the crude mixture brings new understanding to this widely used compound class. It is a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.