Synthesis and Investigation of Perfluorinated Polystannanes

Two fluorinated tetraaryl stannanes, 1 and 2 were synthesized in good yields. X-ray crystallography revealed deviation from ideal tetrahedral geometry with C-Sn-C bond angles between 107.89°-112.7° for 1 and 104.69°-120.76° for 2. Dichlorides 4 and 5 were synthesized using a redistribution reaction between SnC1₄ and 1-2. These dichlorides also deviated from tetrahedral geometry with bond angles between 101.79°-128.44° for 4 and 99.23°-125.9° for 5. Polymerizaton of 4 and 5 by Wurtz coupling produced polymers 10 and 11. Absolute molecular weights in the range of 1.16 x 10⁵-2.92 x 10⁷ Da was estimated for 10 and 1.47 x 10⁵ Da for 11. UV/VIS spectroscopy gave values of 332 nm and 328 nm that are blue shifted to other polystannanes. The unexpected cleavage of a tin-aryl bond produced tin trihydrides 8 and 9. Polymerization of 8-9 produced the network polymers 12 and 13 with [wavelength]max values of 354 nm and 350 nm.