Alkyltin Keggin Clusters Templated by Sodium

Abstract

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.

Assembly of high-nuclearity Sn26, Sn34-oxo clusters: solvent strategies and inorganic Sn incorporation

“…One common way is to use organotin as precursors to react with carboxylate ligands in organic solvents, such as benzene, toluene, and alcohols 23–27. To date, the representative structural types of TOCs are characterized by cubic [ n -BuSn(O)O 2 P( t -Bu) 2 ] 4 ,28 hexameric drum {R′SnO(O 2 CR)} 6 ,29 ladder [(R′Sn(O)O 2 CR) 2 R′Sn(O 2 CR) 3 ] 2 ,30 and Keggin-type alkyltins 31–33. However, despite these advances, the structural diversity of tin-oxo clusters is still less developed compared to transition-metal oxo clusters.…”

Photo-induced Fragmentation of a Tin-oxo Cage Compound

“…The mechanism behind the solubility change of the tin-oxo cages (and related materials) is still under investigation. Knowledge of the chemical mechanism is paramount for the design of novel metal-containing materials with even better resist performance [13]. Ideally, one would expose the photoresist to EUV radiation and analyze the reaction products afterwards, or even in situ.…”

MeSi(CH2SnRO)3 (R=Ph, Me3SiCH2): Building Blocks for Triangular‐Shaped Diorganotin Oxide Macrocycles

“…Compound 2 easily converted to the tris(mono) and tris(di) halogenated derivatives MeSi(CH 2 SnIPh 2 ) 3 (3)a nd Me-Si(CH 2 SnI 2 Ph) 3 (4)b yi ts reaction with three,r espectively six molar equiv of elemental iodine (Scheme 2). Thet reatment of 3 with three molar equiv trimethylsilylmethylmagnesium chloride,M e 3 SiCH 2 MgCl, gave the corresponding tetraorganotin derivative MeSi[CH 2 Sn(CH 2 SiMe 3 )Ph 2 ] 3 (5) which, by reaction with six molar equiv elemental iodine, provided MeSi[CH 2 Sn(CH 2 SiMe 3 )I 2 ] 3 (6). Compound 2 is ac olourless crystalline material while its derivatives 3-6 represent slightly yellow oils.A ll compounds show good solubility in common organic solvents such as CH 2 Cl 2 ,CHCl 3 , THF,a nd CH 3 CN.T he Supporting Information contains the analytical data including the molecular structure of 2 (Figure S12) as determined by single crystal X-ray diffraction analysis.T he data are as expected and confirm unambiguously the identities of compounds 2-6.…”