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 ‐XC 6 F 4 CNSSN (X=F, Cl, Br, I, CN) with TEMPO afforded the 2 : 1 cocrystals [ p ‐XC 6 F 4 CNSSN] 2 [TEMPO] ( 1 – 5 ) whose structures all reflect a common S 4 ⋅⋅⋅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 [C 6 F 5 CNSSN] 2 [TEMPO] supramolecular motif from [C 6 F 5 CNSSN] 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 S 4 ⋅⋅⋅O interaction.
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How this classification was reachedexpand
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 | 0.002 | 0.002 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.003 |
| Bibliometrics | 0.001 | 0.002 |
| Science and technology studies | 0.002 | 0.002 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.003 | 0.002 |
| Research integrity | 0.001 | 0.007 |
| 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; both teacher heads agree on what is shown here.
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".