Synthesis and Reversible Redox Properties of an Electron-Rich Polyferrocenylsilane with <i>tert</i>-Butyl Substituents on the Cyclopentadienyl Ligands
Bibliographic record
Abstract
The strained sila-[1]ferrocenophane monomer Fe(η-C 5 H 3 t Bu) 2 SiPh 2 ( 5 ) was synthesized and polymerized via thermal ring-opening polymerization (ROP) both in the melt and in solution to give the soluble high-molecular-weight polyferrocenylsilane (PFS) [Fe(η-C 5 H 3 t Bu 2 ) 2 SiPh 2 ] n, 7 ( M n = 5.2 × 10 4 −1.7 × 10 6 Da, PDI = 1.38−1.99). Both monomer 5 and polymer 7 were structurally characterized by 1 H, 13 C, and 29 Si NMR spectroscopy and elemental analysis. The electronic structure and electrochemical properties of the monomer 5 and the polymer 7 were investigated by UV−vis spectroscopy and cyclic voltammetry. The oxidation potentials were shifted to more negative values relative to non-methylated or methylated analogues, indicating that the electron-donating effect of the t Bu group is transmitted to the iron center. Polymer 7 exhibited two reversible redox waves with a redox coupling, Δ E 1/2, of 0.33 V, which is indicative of appreciable Fe···Fe interactions along the polymer backbone. The resiliency of 7 toward the redox processes was probed by measuring the molecular weights before photooxidation or chemical oxidation (with tetracyanoethylene (TCNE) or tris(4-bromophenyl)ammoniumyl hexachloroantimonate) and after subsequent reduction of the oxidized polymers to the neutral forms by using bis(pentamethylcyclopentadienyl)iron(II). Significantly, unlike the previous studies of oxidized PFS homopolymers, soluble polymeric salts were obtained even for a high degree of oxidation, and these were characterized by UV−vis and IR spectroscopy. GPC measurements demonstrated the excellent redox resiliency of polyferrocenylsilane 7 to redox cycling as no appreciable decline in molecular weight was apparent for degrees of oxidation of up to 50%.
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How this classification was reachedexpand
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 | 0.000 | 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 teacher head, 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".