Triplet state structure–property relationships in a series of platinum acetylides: effect of chromophore length and end cap electronic properties
Bibliographic record
Abstract
To develop quantitative structure-spectroscopic property relationships in platinum acetylides, we investigated the triplet state behavior of nominally centrosymmetric chromophores trans-Pt(PBu3)2(C[triple bond, length as m-dash]C-Phenyl-X)2, where X = diphenylamino, NH2, OCH3, t-Bu, CH3, H, F, benzothiazole, CF3, CN, and NO2. We measured ground state absorption, phosphorescence, excitation and triplet state absorption spectra and triplet lifetimes. By DFT we calculated the phosphorescence emission energy (ET), the spin density on the end cap (SD(X)), triplet state geometry and the distance between the triplet centroid and the central platinum atom (RS-Pt(X)). Compounds with electron-donating X have smaller triplet state lifetime, blue-shifted phosphorescence and larger triplet potential energy surface displacement associated with the C[triple bond, length as m-dash]C bond. Compounds with electron-withdrawing X have larger triplet lifetime, red-shifted phosphorescence and smaller triplet potential energy surface displacement associated with the C[triple bond, length as m-dash]C bond. The range of spin-orbit-coupling between the platinum atom and the triplet centroid was determined to be 6 Å. The quantity RS-Pt is shown to be a linear function of one-dimensional well length calculated from experimental ET. The multiple examples demonstrate RS-Pt is a useful descriptor for analyzing triplet state behavior.
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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 | 0.001 |
| 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".