Charge Transfer and Delocalization in Conjugated (Ferrocenylethynyl)oligothiophene Complexes
Bibliographic record
Abstract
A series of conjugated mono(ferrocenylethynyl)oligothiophene and bis(ferrocenylethynyl)oligothiophene complexes have been prepared. The cyclic voltammograms of the complexes all contain a reversible ferrocene oxidation wave and an irreversible oligothiophene-based wave. The potential difference between the two waves (Δ E ) varies from 0.38 to 1.12 V, depending on the length and substitution of the oligothiophene group. Several of the mono(ferrocenylethynyl)oligothiophene complexes couple when oxidized, resulting in the deposition of a redox-active film on the electrode surface. In solution, electrochemical oxidation of the Fe II centers yields the corresponding monocations and dications, which exhibit oligothiophene-to-Fe III charge-transfer transitions in the near-IR region. The band maxima of these low-energy transitions correlate linearly with Δ E, while the oscillator strengths show a linear correlation with negative slope with Δ E . The complexes with similar charge-transfer transition dipole lengths show an increase in the extent of charge delocalization with smaller Δ E . Comparisons between complexes with different length oligothiophene ligands show that a reduction in Δ E results either in greater delocalization of charge or in charge being delocalized further along the rigid oligothiophene ligand. These results have important implications in understanding charge delocalization in metal-containing polymers.
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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".