A pentacene intermediate via formal intramolecular photoredox of a 6,13-pentacenequinone in aqueous solution
Bibliographic record
Abstract
The formal intramolecular photoredox reaction (or tandem phototautomerizations) of aromatic ketones in aqueous solution discovered in our laboratory has been extended to a number of acenequinones. In particular, we were interested in whether the photoredox reaction could be applied to 2-(hydroxymethyl)-6,13-pentacenequinone (4), which would result in 2-formyl-6,13-dihydroxypentacene (10) and hence offer a photochemical method for synthesizing a pentacene derivative. Whereas a number of acenequinones displayed a range of photoredox reactivity, photolysis of 4 in acidic aqueous solution (pH < 3) resulted in a clean intramolecular photoredox reaction, via an enol intermediate, to give 10 (green compound; Φ ~ 0.2 at pH 1), which was too reactive for isolation or trapping by standard ArOH trapping agents such as acetic anhydride. These reactions may be viewed as a one-way photochemical intramolecular “redox switch” from quinone to hydroquinone with concurrent oxidation of an attached hydroxymethyl (alcohol) moiety. Without the attached alcohol moiety, these acenequinones are photostable in aqueous solution. The trend in observed relative reactivity may be partially rationalized by examining changes in molecular orbital coefficients observed in the calculated HOMOs and LUMOs (at the AM1 level).Key words: pentacene, acenequinones, photoredox, enol, acid catalysis.
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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 | 0.000 |
| 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 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".