Robust S<sub>4</sub>⋅⋅⋅O Supramolecular Synthons: Structures of Radical‐Radical Cocrystals [<i>p</i>‐XC<sub>6</sub>F<sub>4</sub>CNSSN]<sub>2</sub>[TEMPO] (X=F, Cl, Br, I, CN)
Bibliographic record
Abstract
Abstract Cocrystallization of the dithiadiazolyl (DTDA) radicals p‐XC6F4CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [p‐XC6F4CNSSN]2[TEMPO] (1–5) whose structures all reflect a common S4⋅⋅⋅O supramolecular motif. The nature of this interaction was probed by DFT calculations (M06/aug‐cc‐pVDZ) on 1 which revealed that the enthalpy of formation of the [C6F5CNSSN]2[TEMPO] supramolecular motif from [C6F5CNSSN]2 and TEMPO is substantial (−54.0 kJ mol−1). Electronic structure calculations revealed a TEMPO‐based doublet S= configuration as the ground state with limited spin density on the DTDA rings (2.4 %). The corresponding spin quartet state is +78.9 kJ mol−1 higher in energy. An atoms‐in‐molecules analysis reveals four bond critical points (BCPs) between the TEMPO O and the DTDA S atoms as well as additional BCPs between selected DTDA S atoms and methyl H atoms of the TEMPO molecule. Herein, the structures of 2–5 are considered within the context of a hierarchical view of competing and complementary intermolecular interactions; in particular, the established supramolecular CN⋅⋅⋅S−S synthon is sacrificed in order to form the new S4⋅⋅⋅O interaction.
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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) | 0.002 | 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".