Metal-containing polymers bearing pendant nickel(II) complexes of Goedken's macrocycle
Bibliographic record
Abstract
The design, synthesis, and polymerization of a norbornene-based monomer bearing a nickel(II) complex of Goedken's macrocycle (endo-13) and the characterization of the resulting polymer are described. Detailed studies of the ring-opening metathesis polymerization of endo-13 using the 3-bromopyridine adduct of Grubbs' 3rd generation catalyst revealed that the polymerization shares many characteristics associated with a living polymer, but deviated from ideal behavior when high degrees of polymerization were targeted. The installation of a 3-hexylphenyl substituent at the macrocyclic backbone allowed for the realization of soluble polymers (14) and shut down an oxidative dimerization pathway commonly associated with metal complexes of Goedken's macrocycle. The cyclic voltammogram of the polymer 14 was comprised of two one-electron oxidation waves (0.21 V and 0.70 V relative to ferrocene/ferrocenium) associated with the stepwise oxidation of the macrocyclic ligand backbone and a one electron reduction wave associated with the reduction of nickel(II) to nickel(I) (-2.07 V). Solution and solid-state UV-vis absorption spectra recorded for polymer 14 revealed a strong p®p* absorption (lmax = 390 nm) and a ligand-to-metal charge transfer band (lmax = 590 nm) typical of nickel(II) complexes of Goedken's macrocycle, and confirmed the absence of macrocycle-macrocycle interactions. This work has ultimately led to the development of a controlled polymerization route to a rare example of a side-chain nickel-containing polymer with potentially useful properties.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.002 | 0.002 |
| Research integrity | 0.000 | 0.001 |
| 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".