Redox Chemistry of Nickelocene-Based Monomers and Polymers
Bibliographic record
Abstract
The oxidation of [ n ]nickelocenophanes [Ni(η 5 -C 5 H 4 ) 2 (CH 2 ) 3 ] ( 3 ), [Ni(η 5 -C 5 H 4 ) 2 (SiMe 2 ) 2 ] ( 10 ), [Ni(η 5 -C 5 H 4 ) 2 (SiMe 2 ) 2 O] ( 11 ), [Ni(η 5 -C 5 H 4 ) 2 (CH 2 ) 4 ] ( 12 ), and poly(nickelocenylpropylene) [Ni(η 5 -C 5 H 4 ) 2 (CH 2 ) 3 ] n ( 4 ) to both the monocationic and dicationic species was investigated in dichloromethane by cyclic voltammetry (CV) and square-wave voltammetry. The presence of acetonitrile on the oxidation potentials of 3 in dichloromethane was also investigated by CV. The [ n ]nickelocenophanes 3 and 10 – 12 exhibited two single-electron Nernstian redox processes, and the monocations [3] +, [10] +, [11] +, and [12] + were isolable as [B(C 6 F 5 ) 4 ] − salts after chemical oxidation, and were structurally characterized. Ni–Cp cent distances in all four monomers decreased upon oxidation, with a structural distortion manifested in the ring-tilt angle, α, among other angles. CV studies of the reversible first oxidation process to the polyelectrolyte {[Ni(η 5 -C 5 H 4 ) 2 (CH 2 ) 3 ] + } n ( [4] n + ) were used to estimate the molecular weight of the polymeric material ( M w = 5300 g mol –1 ) by comparing its diffusion coefficient with that of a monomeric analogue, and the second electrochemical oxidation of polymer 4 was found to be only partially chemically reversible.
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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".