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 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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 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 itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, 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".