Electrogenerated Chemiluminescence. 74. Photophysical, Electrochemical, and Electrogenerated Chemiluminescent Studies of Selected Nonplanar Pyrenophanes
Bibliographic record
Abstract
We report here the photophysical, electrochemical, and electrogenerated chemiluminescent studies of four new pyrenophanes. Comparison with the cyclic voltammogram obtained using the planar parent compound, pyrene, showed these bent-pyrene-containing cyclophanes have a shift in the thermodynamic reduction potentials to more negative values. AM1 semiempirical calculations support such findings in which the LUMO energy increased with the degree of nonplanarity. The HOMO energy, however, remained essentially unchanged for all the compounds in this study. The nonplanarity in these compounds resulted in a substantial decrease in fluorescence quantum yield as well as a slight red shift in both the absorption and emission spectra. In addition, unlike pyrene, no excimer emission was evident in the fluorescence spectra even at concentrations as high as 1 mM. However, the ECL spectra of all four pyrenophanes, produced by generating the anion radical in the presence of benzoyl peroxide as a coreactant, showed broad “excimer-like” emission in addition to the monomer emission observed at shorter wavelengths.
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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".