Silsesquioxane Models for Geminal Silica Surface Silanol Sites. A Spectroscopic Investigation of Different Types of Silanols
Why this work is in the frame
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Bibliographic record
Abstract
The incompletely condensed monosilylated silsesquioxanes (c-C5H9)7Si7O9(OSiRR'2)(OH)2 (SiRR'2 = SiMe3, SiMe2C(H)CH2, SiMePh2) were reacted with SiCl(4) in the presence of an amine which yielded the dichloro compounds (c-C5H9)7Si7O9(OSiRR'2)O2SiCl2 (1-3). These compounds could be hydrolyzed into the corresponding silsesquioxanes containing geminal silanols, (c-C5H9)7Si7O9(OSiRR'2)O2Si(OH)2 (4-6). At elevated temperatures, the geminal silsesquioxanes 4 and 5 undergo condensation reactions and form the closed-cage silsesquioxane monosilanol, (c-C5H9)7Si8O12(OH). The more sterically hindered geminal silsesquioxane 6 undergoes in solution intermolecular dehydroxylation, yielding the thermodynamically stable dimeric disilanol, [(c-C5H9)7Si7O9(OSiMePh2)(O2Si(OH)-)]2-(mu-O) (7). NMR and FT-IR studies show that the two silanols of the geminal silsesquioxanes 4-6 are different from each other with respect to hydrogen bonding, both in solution and in the solid state. Hydrogen bonding of the geminal silanol-containing silsesquioxanes was examined and compared to hydrogen bonding in silsesquioxanes possessing vicinal or isolated silanol groups. The relative Brønsted acidity of the geminal silanols was determined using pK(ip) (ion-pair acidity) measurements in THF with UV-vis. These acidities were compared with those of other silsesquioxanes containing silanol groups. Acidities of 4-6 were found to be among the lowest known for silsesquioxanes.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it