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Alkyltin Keggin Clusters Templated by Sodium
Author(s) -
Saha Sumit,
Park DeokHie,
Hutchison Danielle C.,
Olsen Morgan R.,
Zakharov Lev N.,
Marsh David,
GobernaFerrón Sara,
Frederick Ryan T.,
Diulus J. Trey,
Kenane Nizan,
Herman Gregory S.,
Johnson Darren W.,
Keszler Douglas A.,
Nyman May
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201701703
Subject(s) - polyoxometalate , cluster (spacecraft) , counterion , cationic polymerization , crystallography , chemistry , materials science , ion , catalysis , polymer chemistry , organic chemistry , computer science , programming language
Dodecameric (Sn 12 ) 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 4 (BuSn) 12 (OH) 3 (O) 9 (OCH 3 ) 12 (Sn(H 2 O) 2 )] (β‐NaSn 13 ). SAXS, NMR, and ESI MS differentiate β‐NaSn 13 , Sn 12 , 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 13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.