Phosphorus Copies of PPV: π-Conjugated Polymers and Molecules Composed of Alternating Phenylene and Phosphaalkene Moieties
Bibliographic record
Abstract
A new class of pi-conjugated macromolecule, poly(p-phenylenephosphaalkene) (PPP), is reported. PPPs are phosphorus analogues of the important electronic material poly(p-phenylenevinylene) (PPV) where P=C rather than C=C bonds space phenylene moieties. Specifically, PPPs [-C(6)R(4)-P=C(OSiMe(3))-C(6)R'(4)-C(OSiMe(3))=P-](n)() (1: R = H, R' = Me; 11: R = Me, R' = H) were synthesized by utilizing the Becker reaction of a bifunctional silylphosphine, 1,4-C(6)R(4)[P(SiMe(3))(2)](2), and diacid chloride 1,4-C(6)R'(4)[COCl](2). Several model compounds for PPP are reported. Namely, mono(phosphaalkene)s R-P=C(OSiMe(3))-R' (4: R = Ph, R' = Mes; 7: R = Mes, R' = Ph), C-centered bis(phosphaalkene)s R-P=C(OSiMe(3))-C(6)R'(4)-C(OSiMe(3))=P-R (5: R = Ph, R' = Me; 8: R = Mes, R' = H), and P-centered bis(phosphaalkene)s R-C(OSiMe(3))=P-C(6)R'(4)-P=C(OSiMe(3))-R (6: R = Mes, R' = H; 10: R = Ph, R' = Me). Remarkably, selective Z-isomer formation (i.e., trans arylene moieties) is observed for PPPs when bulky P-substituents are employed while E/Z-mixtures are otherwise obtained. X-ray crystal structures of Z-7, Z,Z-8, and Z,Z-10 suggest moderate pi-conjugation. The twist angles between the P=C plane and unsubstituted arenes are 16 degrees -26 degrees , while those between the P=C plane and methyl-substituted arenes are 59 degrees -67 degrees . The colored PPPs and their model compounds were studied by UV/vis spectroscopy, and the results are consistent with extended pi-conjugation. Specifically, weakly emissive polymer E/Z-1 (lambda(max) = 338 nm) shows a red shift in its absorbance from model E/Z-4 (lambda(max) = 310 nm), while a much larger red shift is observed for Z-11 (lambda(max) = 394 nm) over Z-7 (lambda(max) = 324 nm).
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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) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".