Electron spin polarization in the triplet state of methoxy-substituted phosphorus(V) tetraphenyl porphyrins
Bibliographic record
Abstract
• Electron spin polarization is an important property of photoexcited triplet states • The initial spin polarization of phosphorus(V) porphyrins varies with substituents • Net polarization develops as a result of the dynamic Jahn-Teller effect • Net polarization is crucial for the polarization of distant radicals Photoexcited triplet states of porphyrins are of great relevance in various applications due to their high yield, long lifetime, and strong electron spin polarization. This study delves into properties and spin dynamics of the triplet state of a series of hypervalent phosphorus(V) porphyrins. Transient Electron Paramagnetic Resonance (TrEPR) measurements, supported by quantum chemical calculations as well as by optical absorption/luminescence experiments, reveal that, unlike singlet states, the lowest triplet state does not exhibit charge-transfer (CT) character upon photoexcitation. However, the presence of excited CT singlet states alters the intersystem crossing in phosphorus(V) porphyrins, leading to a sign change in the initial multiplet polarization of the photoexcited triplet state. TrEPR results further demonstrate that significant net polarization develops in the triplet states of the phosphorus(V) porphyrins due to the dynamic Jahn-Teller effect. Yet, this effect remains largely unaffected by differences in their molecular structures.
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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 | 0.002 | 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) | 0.000 | 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".