Cucurbit[<i>n</i>]urils (<i>n</i>= 5–8): A Comprehensive Solid State Study
Bibliographic record
Abstract
Cucurbit[ n ]urils (CB[ n ], n = 5–8) have been prepared, separated, and purified, and the structure of their solid state assemblies has been addressed. A number of general features were identified which are of interest to understand some peculiar properties of cucurbiturils (solubility, aggregation, assembly, transformation to porous crystals, influence of air humidity). CB[5], CB[6], and CB[8] were isolated as hydrate crystals whose structures were found to show a strong tendency of the macrocycles to interpenetrate. A self-closing effect was rationalized in terms of multiple weak CH···O interactions between the macrocycles, the degree of which is discussed in detail. Solid state cross polarization magic angle spinning (CP-MAS) 13 C NMR spectra obtained at 900 MHz were correlated with the crystal structures. An odd–even effect in the crystallinity of thermally treated CB samples (CB[5] and CB[7] amorphous, CB[6] and CB[8] crystalline) was observed, which is reflected in differences in water solubility (CB[5] and CB[7] are water-soluble, whereas CB[6] and CB[8] are only very scarcely so). This may be explained by a less efficient self-association for CB[5] and CB[7] as compared with CB[6] and CB[8], which is reflected in the number of inter-cucurbituril CH···O interactions per cucurbituril. This leads to a more favorable solvation for the CBs having an odd symmetry, whereas those with even symmetry prefer to self-associate in a manner ultimately leading to crystallization. We also propose an explanation for the presence of anions (Cl – ) inside some cucurbituril materials, whose cavity is often considered hydrophobic. Furthermore, it is demonstrated that large quantities of the very stable microporous CB[6] crystals (which have the R 3̅ channel structure) can be obtained very easily by a simple thermal treatment of the hexagonal crystals of CB[6] ( P 6/ mmm structure) obtained directly from the initial reaction used to synthesize the various CB[ n ]. The micromorphology of the CB[ n ] powders was established using scanning electron microscopy (SEM), and the tendency of each material to absorb water from the atmosphere was demonstrated by thermogravimetric analyses (TGA).
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".