Large Polyhedral Oligomeric Silsesquioxane Cages: The Isolation of Functionalized POSS with an Unprecedented Si₁₈ O₂₇...

The synthesis of organo-functionalized polyhedral oligomeric silsesquioxanes (POSS, (R-SiO_1.5 )_n , T_n ) is an area of significant activity. To date, T₁₄ is the largest such cage synthesized and isolated as a single isomer. Herein, we report an unprecedented, single-isomer styryl-functionalized T₁₈ POSS. Unambiguously identified among nine possible isomers by multinuclear solution NMR (¹ H, ¹³ C, and ²⁹ Si), MALDI-MS, FTIR, and computational studies, this is the largest single-isomer functionalized T_n compound isolated to date. A ring-strain model was developed to correlate the ²⁹ Si resonances with the number of 6-, 5-, and/or 4-Si-atom rings that each non-equivalent Si atom is part of. The model successfully predicts the speciation of non-equivalent Si atoms in other families of T_n compounds, demonstrating its general applicability for assigning ²⁹ Si resonances to Si atoms in cage silsesquioxanes and providing a useful tool for predicting Si-atom environments.