A Convenient <i>N</i>-Arylation Route for Electron-Deficient Pyridines: The Case of π-Extended Electrochromic Phosphaviologens
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Bibliographic record
Abstract
A simple and representative procedure for the synthesis of N,N'-diarylated phosphaviologens directly from both electron-rich and electron-poor diaryliodonium salts and 2,7-diazadibenzophosphole oxide is reported. The latter are electron-deficient congeners of the widely utilized N,N'-disubstituted 4,4'-bipyridinium cations, also known as viologens, that proved to be inaccessible by the classical two-step route. The single-step preparation method for phosphaviologens described herein could be extended to genuine viologens but reached its limit when sterically demanding diaryliodonium salts were used. The studied phosphaviologens feature a significantly lowered reduction threshold as compared to all other (phospha)viologens known to date due to the combination of an extended π-system with an electron deficient phosphole core. In addition, a considerably smaller HOMO-LUMO gap was observed due to efficient π-delocalization across the phosphaviologen core, as well as the N-aryl substituents, which was corroborated by quantum chemical calculations. Detailed characterizations of the singly reduced radical species by EPR spectroscopy and DFT calculations verified delocalization of the radical over the extended π-system. Finally, to gain deeper insight into the suitability of the new compounds as electroactive and electrochromic materials, multicolored proof-of-concept electrochomic devices were manufactured.
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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 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 it