Binuclear Ruthenium Complexes of a Neutral Radical Bridging Ligand. A New “Spin” on Mixed Valency
Bibliographic record
Abstract
The electronic structures of (LX)2Ru(Vd)Ru(LX)2 complexes (Vd = 1,5-diisopropyl-3-(4,6-dimethyl-2-pyrimidinyl)-6-oxoverdazyl radical; LX = acac (acetylacetonate) or hfac (hexafluoroacetylacetonate)) in multiple charge states have been investigated experimentally and computationally. The main focus was to probe the consequences of the interplay between the ruthenium ions and the redox-active verdazyl ligand for possible mixed-valent behavior. Cyclic voltammetry studies reveal one reversible reduction and one reversible oxidation process for both complexes; in addition the acac-based derivative possesses a second reversible oxidation. Analysis of a collection of experimental (X-ray structures, EPR, electronic spectra) and computational (TD-DFT (PCM)) data reveal that the ruthenium ancillary ligands (acac vs hfac) have dramatic consequences for the electronic structures of the complexes in all charge states studied. In the hfac series, the neutral complex is best regarded as a binuclear Ru(II) species bridged by a neutral radical ligand. Reduction to give the anionic complex takes place on the verdazyl ligand, whereas oxidation to the cation (a closed shell species) is shared between Vd and ruthenium. For the acac-based complexes, the neutral species is most accurately represented as a Ru(II)/Ru(III) mixed valent complex containing a bridging verdazyl anion, though some bis(Ru(II))-neutral radical character remains. The monocation complex contains a significant contribution from a "broken symmetry" singlet diradical structure, best represented as a bis-Ru(III) system with an anionic ligand, with significant spin coupling of the two Ru(III) centers via the Vd(-1) ligand (calculated J = -218 cm(-1)). The dication, a spin doublet, consists of two Ru(III) ions linked (and antiferromagnetically coupled) to the neutral radical ligand. Computed net σ- and π-back-donation, spin densities, and orbital populations are provided. Time dependent DFT is used to predict the optical spectra and assign experimental data.
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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) | 0.002 | 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 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".