Anionic polymerisation of phosphaalkenes bearing polyaromatic chromophores: phosphine polymers showing “turn-on” emission selectively with peroxide
Bibliographic record
Abstract
Three new phosphaalkenes bearing C-aryl chromophores, MesPCPh(Ar) (1a: Ar = 1-naphthyl, 1b: 9-phenanthryl, 1c: 5-dibenzosuberenyl; Mes = 2,4,6-trimethylphenyl), are reported. Each phosphaalkene was characterised by multinuclear NMR spectroscopy (1H, 13C, 31P), X-ray crystallography, mass spectrometry, UV/Visible spectroscopy and elemental microanalysis (1b and 1c). Monomers 1a and 1b were successfully polymerised using anionic methods of initiation (n-BuLi: 5 and 1.5 mol%, respectively) to afford poly(methylenephosphine)s (PMPs: 2a: Mn = 15 100 Da, PDI = 1.14; 2b: Mn = 17 500 Da; PDI = 1.39). Detailed NMR spectroscopic analysis of polymer 2a revealed that its microstructure is primarily composed of [P(CHPhNaph)–(4,6-Me2C6H2)–2-CH2]n units rather than the expected [P(Mes)–CPh2]n. Functional polymer 2a was oxidised to the phosphine oxide 2a·O or phosphine sulfide 2a·S, and coordinated to borane to afford 2a·BH3 or gold(I) to afford 2a·AuCl. Significantly, 2a shows “turn-on” emission properties selectively as its oxide 2a·O (λex = 286 nm; λem = 342 nm) which is prepared by treatment with hydrogen peroxide.
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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 | 0.001 |
| Science and technology studies | 0.000 | 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 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".