Extended Tetrathiafulvalene Multi‐Redox Systems Incorporating 4,5‐Dihydroazuleno[2,1,8‐<i>ija</i>]azulene Cores
Bibliographic record
Abstract
The introduction of 4,5-dihydroazuleno[2,1,8-ija]azulene as a central core between two 1,4-dithiafulvene (DTF) units provides a novel class of extended tetrathiafulvalene (TTF) electron donors. Herein we present the synthesis of such compounds with the azulenoazulene further expanded by annulation to benzene, naphthalene, or thiophene rings. Moreover, unsymmetrical donor-acceptor chromophores with one DTF and one carbonyl at the central core are presented. The effect of the odd-membered rings of the polycyclic aromatic hydrocarbon cores on the geometrical features and the extent of bond conjugation in these systems were investigated by UV/Vis absorption spectroscopy, (spectro)electrochemical studies, X-ray and electron diffraction, and computational studies. Altogether these studies reveal that, upon oxidation, the non-planar core of the bis(benzo)-fused dihydro-azulenoazulene-extended TTF generates a large 22π-aromatic system (together with two 6π-aromatic 1,3-dithiolium appendages) characterized by significant bond length equalizations. The dication formed by oxidation is EPR silent, indicating a singlet ground state. Computations reveal that the closed-shell singlet species and its open-shell singlet counterpart are nearly degenerate and of lower energy than a triplet species. According to cyclic voltammetry, the compounds can be oxidized further and present multi-redox systems.
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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".