Conjugated Organometallic Polymer Containing a Redox-Active Center
Bibliographic record
Abstract
The new conjugated organometallic polymer (-spacer-C[triple bond]C-Pt(PBu3)2-C[triple bond]C-)n (3; spacer = para-bis(diphenyl(tetramethyl)quinone diimine) and the cyclic mononuclear model complex, spacer'-C[triple bond]C-Pt(PEt3)2-C[triple bond]C x CuCl (4; spacer' = ortho-diphenyl-2,3,5,6-tetramethyl-1,4-benzoquinone diimine) were synthesized from the 1:1 condensation of the corresponding diethynyl ligands (2-para and 2-ortho (para- and ortho-diethynyl-diphenyl-2,3,5,6-tetramethylquinone diimine), respectively), with the trans-Pt(PBu3)2Cl2 for polymer 3 and cis-Pt(PEt3)2Cl2 for 4. The materials were characterized by GPC, DSC, ATG, and electrochemistry for polymer 3, and by X-ray diffraction for 4. Polymer 3 exhibits a M(n) of 18500, M(w) of 25000 with a PD of 1.37. The trans-geometry about Pt in polymer 3 was confirmed by 31P NMR and IR/Raman spectroscopy. The cyclic voltammogram study on the model complex trans-Pt(PBu3)2(C[triple bond]CPh)2, spacer 1-para (Me3Si-C[triple bond]C-R-C[triple bond]C-SiMe3; R = para-diphenyl-2,3,5,6-tetramethyl-1,4-benzoquinone diimine) and polymer 3 demonstrated that polymer 3 in the presence of trifluoroacetic acid (TFA) exhibits a quasi reversible 2-electron reduction process centered at 0.48 V versus SCE corresponding to the reduction of the protonated quinone diimine unit into the corresponding diamine. The UV-vis spectra of the spacer 2-para (440 nm) and polymer 3 (502 nm) are characterized by red-shifted charge transfer (CT) absorptions (C6H4C[triple bond]C --> quinone diimine for 2-para; and (C6H4C[triple bond]C)2Pt --> quinone diimine for polymer 3). These assignments are corroborated by density-functional theory (DFT) and time-dependent density-functional theory (TDDFT) computations. Polymer 3 is not luminescent in the solid state or in solution at 77 K and 298 K.
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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) | 0.002 | 0.001 |
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".