Modulating the generation of long-lived charge separated states exclusively from the triplet excited states in palladium porphyrin–fullerene conjugates
Bibliographic record
Abstract
This study demonstrates molecular engineering of a series of donor-acceptor systems to allow control of the lifetime and initial spin multiplicity of the charge-separated state. By tuning the rate of intersystem crossing (ISC) and the donor-acceptor distance, electron transfer can be made to occur exclusively from the triplet excited state of the electron donor resulting in long-lived charge separation. To achieve this, three new palladium porphyrin-fullerene donor-acceptor systems were synthesized. The heavy Pd atom enhances the rate of ISC in the porphyrin and the rates of electron and energy transfer are modulated by varying the redox potential of the porphyrin and the porphyrin-fullerene distance. In the case of the meso-tris(tolyl)porphyrinato palladium(ii)-fulleropyrrolidine, the donor-acceptor distance is relatively long (13.1 Å) and the driving force for electron transfer is low. As a result, excitation of the porphyrin leads to rapid ISC followed by triplet-triplet energy transfer to fullerene. When the fullerene is bound directly to the porphyrin shortening the donor-acceptor distance to 2.6 Å electron transfer from the singlet excited palladium porphyrin leading to the generation of a short-lived charge separated state is the main process. Finally, when the palladium porphyrin is substituted with three electron rich triphenylamine entities, the lower oxidation potential of the porphyrin and appropriate donor-acceptor distance (∼13 Å), lead to electron transfer exclusively from the triplet excited state of palladium porphyrin with high quantum yield. The results show that when electron transfer occurs from the triplet state, its increased lifetime allows the distance between the donor and acceptor to be increased which results in a longer lifetime for the charge separated state.
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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 | 0.000 | 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 | 0.000 |
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".