Stereoselective formation of a meso-diruthenium(ii,ii) complex and tuning the properties of its monoruthenium analogues
Bibliographic record
Abstract
A novel bis(bidentate) ligand dgpm (dgpm = diguanidylpyrimidine) was synthesized by a catalyst-free C-N bond forming reaction in high yield (90%) by microwave-assisted heating. The ligand was coordinated to two [Ru(bpy)2](2+) cores to afford a meso-di-Ru(II,II) complex (1-meso) with high diastereoselectivity over its homochiral form. Three mononuclear ether-functionalized Ru(II) complexes (2: ethoxyether; 3: butoxyether; 4: 2-hydroxy-1-ethoxyether) were also isolated. The ligand and complexes were fully characterized by a variety of techniques including X-ray crystallography. In cyclic voltammetric studies, the complexes exhibit a Ru(III/II) couple, which is ~500 mV less positive than the Ru(III/II) couple in Ru(bpy)3(2+). The (1)MLCT absorption maxima of all the complexes (510-550 nm) are considerably red-shifted as compared to that of Ru(bpy)3(2+) (450 nm). The (3)MLCT emission maxima of complexes 1-meso and 3 are also red-shifted by about 120 nm compared to that of Ru(bpy)3(2+) (620 nm), whereas the corresponding maxima for complexes 2 and 4 are shifted by 75 nm and 25 nm, respectively. These relative trends in redox potentials and (1)MLCT maxima are in good agreement with DFT and TD-DFT calculations, performed for all complexes. Complexes 1-meso and 3 display emission from a Ru(II)-to-bpy (3)MLCT state, which is rarely the emitting state at λ > 700 nm in [Ru(bpy)2(N-N)](2+) complexes when the ancillary ligand is neutral.
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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".