Alkyltin Keggin Clusters Templated by Sodium

  • Authors:
    Sumit Saha (Oregon State Univ.), Deok-Hie Park (Oregon State Univ.), Danielle Hutchison (Oregon State Univ.), Morgan Olsen (Oregon State Univ.), Lev Zakharov (Univ. of Oregon), David Marsh (Univ. of Oregon), Sara Goberna-Ferron (Oregon State Univ.), Ryan T. Frederick (Oregon State Univ.), John T. Diulus (Oregon State Univ.), Nizan Kenane (Oregon State Univ.), Gregory S. Herman (Oregon State Univ.), Darren Johnson (Univ. of Oregon), Douglas Keszler (Oregon State Univ.), May Nyman (Oregon State Univ.)
    Publication ID:
    P091153
    Publication Type:
    Paper
    Received Date:
    22-Jun-2017
    Last Edit Date:
    23-Jun-2017
    Research:
    2438.001 (Oregon State University)

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 b-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(H2O)2)] (b-NaSn13). SAXS, NMR, and ESI MS differentiate b-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, b-NaSn13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.

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