<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 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 | 0.000 | 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 | 0.001 |
| 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 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".