<i>In situ</i> PXRD monitoring the mechanosynthesis of metal–organic halogen-bonded cocrystals
Bibliographic record
Abstract
In the last decade, in situ powder X-ray diffraction (PXRD) monitoring of mechanochemical reactions has become a prominent technique for studying the course and mechanisms of organic and metal-organic solid formation [1]. Following our previous study on mechanochemical syntheses of metal-organic halogen-bonded cocrystals [2], in this work we have investigated mechanosynthesis of cocrystals containing CoCl 2 bzpy 2 (bzpy = 2-benzoylpyridine) and a halogen bond donor, 1,4-diiodotetrafluorobenzene (14tfib), by in situ PXRD. First, we performed experiments in solution, and have unexpectedly obtained three different products: two cocrystals with different metal-organic unit isomers, trans-(CoCl 2 bzpy 2 )(14tfib) 2 and cis-(CoCl 2 bzpy 2 )(14tfib) 2 , and a cocrystal of 1:1 stoichiometry, cis-(CoCl 2 bzpy 2 )(14tfib). In order to determine whether single phases could be prepared, mechanosynthesis of obtained cocrystals was studied by in situ PXRD using synchrotron X-ray radiation. Three different liquid-assisted grinding experiments were monitored: grinding of CoCl 2 bzpy 2 and 14tfib in the 1:2 molar ratio, one-pot grinding of CoCl 2 6H 2 O, bzpy and 14tfib in the 1:2:2 molar ratio and grinding of CoCl 2 bzpy 2 and 14tfib in the 1:1 molar ratio. All three monitored reactions revealed presence of a cocrystal with cis isomer as an intermediate and fast conversions to a final, thermodynamically more stable product, trans-(CoCl 2 bzpy 2 )(14tfib) 2 , in less than 10 min. Single crystal X-ray diffraction experiments reveal that dominant supramolecular interactions in all obtained solids are ICl halogen bonds. In the trans-cocrystal halogen bonds form 2D networks while in ciscocrystals 1D chains are formed.
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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".