Insights into the effect of ketylimine, aldimine, and vinylene group attachment and regiosubstitution on the fluorescence deactivation of fluorene
Bibliographic record
Abstract
The spectroscopic and electrochemical properties of a 9-substituted fluorene ketylimine (3) were investigated and compared with those of its vinylene analogue (4) to determine the origins of the quenched fluorescence of these compounds. The predominate mode of singlet excited state deactivation of the heteroatomic fluorene was found to be internal conversion involving bond rotation. Meanwhile, its carbon counterpart was found to undergo deactivation preferentially by intersystem crossing to form its triplet, which was confirmed by laser flash photolysis. Both 3 and 4 quenched the fluorescence of fluorene with diffusion-controlled rate constants, implying that the singlet excited states of 3 and 4 are also quenched by intramolecular photoinduced electron transfer (PET). This deactivation mode was found to be exergonically favorable (–90 kJ/mol for 3 and –81 kJ/mol for 4) according to the Rehm–Weller equation. The position of the heteroatomic bond on the fluorene moiety was further found to influence the singlet excited state deactivation pathway. The 2-substituted regioisomer decayed predominately by intramolecular PET and its fluorescence can be restored by acid protonation. Conversely, the PET mechanism is a minor deactivation mode for the 9-substituted fluorene derivative and its fluorescence can be enhanced by suppressing bond rotational modes, possible at low temperature and potentially in thin films.
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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".