Phosphorus(V) Porphyrin: A Reductive Electron Quencher in Donor-Acceptor Systems
Bibliographic record
Abstract
Phosphorus(V) porphyrins hold an important place in porphyrin chemistry. The hexacoordinated phosphorus center in these porphyrins has a formal oxidation state of +5 and is, thus, extremely electron deficient. As a result, the midpoint potential for oxidation of the phosphorus(V) porphyrin is shifted to a much higher value (1.66 V for PTPP+) compared to the corresponding free-base porphyrin (1.01 V for H2TPP) or zinc(II) porphyrin (0.79 V for ZnTPP). In addition, the phosphorus center provides two axial sites for the covalently binding of substituents, allowing a greater range of possibilities for attaching donors and acceptors. By exploiting these properties several ‘axial-bonding’ type Donor-Acceptor systems have been prepared consisting of octaethylporphyrinatophosphorus(V) (POEP+) and tertaphenylporphyrinatophosphorus(V) (PTPP+) units. The unique structural topology of the octaethylporphyrinatophosphorus(V) (POEP+) and tertaphenylporphyrinatophosphorus(V) (PTPP+) enabled the construction of mono- and di-substituted phosphorus(V) porphyrin-naphthalene conjugates, respectively. Transient absorption studies revealed rapid deactivation of singlet excited phosphorus(V) porphyrin due to the reductive electron transfer process. I will present some of these examples and discuss their structural, redox, and photophysical properties. Figure 1
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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 | 0.001 | 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 | 0.001 |
| 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 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".