Electrochemical and Photophysical Study of Homoleptic and Heteroleptic Methylated Ru(II) Bis‐terpyridine Complexes
Bibliographic record
Abstract
Abstract In this study, we investigate the impact of N‐methylation on the electronic and photophysical properties of both homoleptic and heteroleptic Ru(II) bis‐terpyridine complexes based on the recently reported ligand 4’‐(4‐bromophenyl)‐4,4’’’ : 4’’,4’’’’‐dipyridinyl‐2,2’ : 6’,2’’‐terpyridine (Bipytpy), with pyridine substituents in the 4‐ and 4’’‐position. The first reduction of the methylated complexes takes place at the pyridinium site and is observed as multi‐electron process. Following N‐methylation, the complexes exhibit higher luminescence quantum yields and longer excited‐state lifetimes. Interestingly, the photophysical properties of the heteroleptic and homoleptic complexes are rather similar. TD‐DFT calculations support the experimental results. Furthermore, the complexes are tested as photosensitizers for photocatalytic hydrogen production, as the parent complex 1 [Ru(Bipytpy)(Tolyltpy)](PF6)2 (Tolyltpy: 4′‐tolyl‐2,2′ : 6′,2′’‐terpyridine) was recently shown to be active and highly stable under photocatalytic conditions. However, the methylated complexes reported herein are inactive as photosensitizers under the chosen conditions, presumably due to loss of the methyl groups, converting them to the non‐methylated parent complexes.
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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 | 0.001 | 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".