Soluble Poly(ferrocenylenevinylene) with<i>t</i>-Butyl Substituents on the Cyclopentadienyl Ligands via Ring-Opening Metathesis Polymerization
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Bibliographic record
Abstract
Soluble poly(ferrocenylenevinylene) (PFV) 6 was synthesized via ring-opening metathesis polymerization (ROMP) of ansa -(vinylene)ferrocene Fe(η-C 5 H 3 t Bu) 2 C 2 H 2 ( 5 ) with t Bu substituents on the cyclopentadienyl (Cp) ligands. Monomer 5 was obtained through intramolecular dicarbonyl coupling of the corresponding ferrocene-dicarbaldehyde, 1,1‘-di- t -butyl-3,3‘-dicarbaldehyde, Fe(η-C 5 H 3 t Bu)(CHO) 2 ( 4 ) in the presence of the McMurry reagent. Both monomer precursor 4 and monomer 5 were structurally characterized by 1 H and 13 C NMR spectroscopy, X-ray crystallography, mass spectrometry, and elemental analysis. ROMP of 5 was investigated using molybdenum-based (Schrock-type) and ruthenium-based (Grubbs-type) initiators under various conditions and was monitored by 1 H NMR spectroscopy. Soluble polymers with low or high molecular weight were obtained and completely characterized. Photolytic and thermal ring-opening polymerizations of 5 were also attempted, but only unreacted monomer was isolated under these conditions. The electronic structure of polymer 6 was explored using UV−vis spectroscopy, and evidence for moderate rather than extensive electron delocalization was revealed. Redox reversibility was probed by cyclic voltammetry (CV) for both monomer 5 and polymer 6 . The electron-donating effect of the t Bu groups substituted to the Cp ligands was signaled by the negative shift of the oxidation potentials, and the electronic interaction between the iron centers in the polymer backbone was also evaluated using CV.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| 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 | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 it