Effects of Halo-Substitution on 2′-Chloro-5′-halo-phenyl-1,2,3,5-dithiadiazolyl Radicals: A Crystallographic, Magnetic, and Electron Paramagnetic Resonance Case Study
Bibliographic record
Abstract
The syntheses and characterization of the aryl-substituted dithiadiazolyls 2′-Cl-5′-X-C 6 H 3 CNSSN • [ 1 (X = F), 2 (X = Cl), 3 (X = Br), 4 (X = I)] are described. In all four cases the radicals adopt distorted stacks of π*−π* dimers with interstack S···X contacts. In 1 (monoclinic P 2/ c ) S···Cl contacts are manifested through a noncrystallographic 3-fold axis forming supramolecular trimers, whereas the interstack S···X contacts in 2 (triclinic P 1̅), 3 and 4 (which form an isostructural pair, orthorhombic Pna 2 1 ) form supramolecular chains. While all the structures adopt π*−π* cis-oid dimer motifs, tuning the halogen modifies the intradimer S···S distance. Variable temperature SQUID magnetometry and X-band continuous-wave electron paramagnetic resonance studies revealed the presence of a thermally accessible triplet state in all cases, with the singlet–triplet separation appearing in the order 1 > 2 > 3 > 4, consistent with a reduction in the overlap integral with increasing intradimer S···S separation. Variable temperature structural studies on both 2 and 4 reveal a structural evolution from a distorted π-stack motif toward a regular π-stacked array on warming. This is particularly pronounced in 2 where the intermolecular S···S separations along the stacking direction converge on a regular 3.6 Å spacing at ambient temperature.
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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".