Experimental and Theoretical Predictors for Redox Potentials of Bispyridinylidene Electron Donors
Bibliographic record
Abstract
Abstract Bispyridinylidenes are neutral organic molecules capable of two‐electron oxidation at a range of redox potentials that are widely tunable by choice of substituent, making them attractive as homogeneous organic reductants and active materials in redox flow batteries. In an effort to readily predict the redox potentials of this important class of compounds, we have developed correlations between the experimental redox potentials and both experimental and theoretical predictors. On the experimental side, we show that multinuclear NMR chemical shifts of related pyridinium ions correlate well with the redox potentials of bispyridinylidenes, with R 2 and standard errors (S) reaching 0.9810 and 0.048 V, respectively, when the 13 C (N‐CH 3 ) and 1 H (ortho) chemical shifts are used together. Theoretical studies of the bispyridinylidenes and their doubly oxidized bipyridinium ions gave a range of predictively valuable equations at various levels of computational cost. This ranged from a simple model using only the E HOMO of the bispyridinylidenes ( R 2 =0.9689; S=0.060 V), to a more computationally intensive model which include solvation effects for both redox states which gave the highest predictive value for all methods ( R 2 =0.9958; S=0.022 V). This work will guide further studies of this important class of molecules.
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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 | 0.000 |
| Open science | 0.000 | 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".