Synthesis, Characterization and Photobiological Studies of Ru(<scp>II</scp>) Dyads Derived from <i>α</i>‐Oligothiophene Derivatives of 1,10‐Phenanthroline
Bibliographic record
Abstract
Abstract Three new bis(2,2′‐bipyridine)‐heteroleptic Ru(II) dyads incorporating thienyl groups (n = 1–3, compounds 1, 2 and 3, respectively) appended to 1,10‐phenanthroline were synthesized and characterized to investigate the impact of n on the photophysical and photobiological properties within the series. All three complexes showed unstructured emission near 618 nm from a triplet metal‐to‐ligand charge transfer (3MLCT) state with a lifetime (τem) of approximately 1 μs. Transient absorption measurements revealed an additional excited state that was nonemissive and long‐lived (τTA = 43 μs for 2 and 27 μs for 3), assigned as a triplet intraligand (3IL) state that was accessible only in 2 and 3. All three complexes were strong singlet oxygen (1O2) sensitizers, with quantum yields (Φ∆) for 2 and 3 being the largest (74–78%), and all three were photocytotoxic to cancer cells with visible light activation in the order: 3 > 2 > 1. Cell‐free DNA photodamage followed the same trend, where potency increased with decreasing 3IL energy. Compounds 2 and 3 also showed in vitro photobiological effects with red light (625 nm), where their molar absorptivities were <100 m−1 cm−1. These findings highlight that Ru(II) dyads derived from α‐oligothiophenes directly appended to 1,10‐phenanthroline—namely 2 and 3—possess low‐lying 3IL states that are highly photosensitizing, and they may therefore be of interest for photobiological applications such as photodynamic therapy (PDT).
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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".