Enhanced Red-Light-Driven Hydrogen Evolution by a Diplatinum Photocatalyst by the Larger Wavefunction Leakage of Iodide Coordinated to the Platinum Center
Bibliographic record
Abstract
The single-molecular photocatalyst Pt2(bpia)Cl3 (bpia = bis(2-pyridylimidoyl)amido), recently proven to promote red-light-driven hydrogen evolution reaction in water via singlet-to-triplet (S-T) transitions (Angew. Chem. Int. Ed., 2025, 64, e202418884), is shown to gain a significantly improved photocatalytic efficiency upon donating iodide instead of chloride to give Pt2(bpia)I3. Upon iodide donation, the absorption and emission energies both show a red shift basically due to destabilization of the HOMO by mixing of the iodide orbitals having essentially higher orbital energies compared to those of chloride. Consequently, the triplet lifetime and the luminescence quantum yield are both decreased by obeying the energy gap law. The unique S-T transition features of Pt2(bpia)Cl3 are preserved in Pt2(bpia)I3 with the excited-state redox properties remaining unchanged. In spite of apparently disadvantageous features induced by the iodide donation, Pt2(bpia)I3 is ascertained to promote the photocatalytic H2 evolution in a considerably higher rate in comparison with Pt2(bpia)Cl3, primarily attributed to the higher reductive quenching efficiency for 3*Pt2(bpia)I3. The observations are rationalized due to the substantially more excellent acceptor characteristics of iodide due to its larger wavefunction leakage required to have a larger electronic coupling factor in driving the outer-sphere electron transfer from the sacrificial electron donor.
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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) | 0.001 | 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".