Neutral and Cationic Cyclopentadienyliron Macromolecules Containing Azo Dyes
Bibliographic record
Abstract
Abstract A number of classes of organoiron polymers containing azo dyes pendent to, or in their backbone have been prepared. The first class includes cationic organometallic polyethers, polythioethers and polynorbornenes incorporating aryl and hetaryl azo dyes. These organometallic polymers were synthesized via nucleophilic aromatic substitution reactions or ring opening metathesis polymerization. The resultant polymers were all brightly colored and displayed excellent solubility in polar organic solvents. Thermal analysis indicated that the polymers were thermally stable with decomplexation of the metal moiety at approximately 235 °C. Photolytic demetallation of the polymers resulted in the decoordination of the cationic cyclopentadienyliron moieties and the formation of organic polymers. The organic polymers displayed lower glass transition temperatures than their cationic organoiron analogues. The second class of polymers is ferrocene based polymers with pendent cationic cyclopentadienyliron moieties. The reaction of arene complexes containing azo dye chromophores and terminal hydroxyl groups with 1,1'-ferrocenedicarbonyl chloride gave rise to triiron complexes with a substituted ferrocene center and two terminal arene complexes containing chloro groups. Nucleophilic aromatic substitution polymerization of these triiron complexes with O- and S-containing nucleophiles followed by photolytic demetallation led to the isolation of neutral ferrocene based polymers containing azo dyes in the backbone. Electrochemical studies of these complexes showed the reduction of the cationic iron moieties at -1.42 V, while the neutral iron species were oxidized at 0.89 V. UV-visible studies showed absorption at 419 nm and a bathochromic shift to 530 nm with the addition of HCl.
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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".