Multicomponent Supramolecular Devices: Synthesis, Optical, and Electronic Properties of Bridged Bis‐dirhodium and ‐diruthenium Complexes
Bibliographic record
Abstract
Abstract Four ruthenium‐ and rhodium‐based metal–metal‐bonded multicomponent systems have been synthesized, and their absorption, redox, spectroelectrochemical and structural properties have been studied. The absorption spectra of the four bis‐dimetallic compounds M 2 LM 2 , where L is a bridging ligand and M is rhodium or ruthenium, exhibit very strong bands in the UV, visible and, for the diruthenium species, near‐IR region. The low‐energy absorption bands are assigned to charge‐transfer transitions involving a metal–metal bonding orbital as the donor and an orbital centered on the bis‐tetradentate aromatic ligands as the acceptor (metal–metal to ligand charge transfer, M 2 LCT). Each compound exhibits reversible bridging‐ligand‐centered reductions at mild potentials and several reversible oxidation processes. The oxidation signals of the two equivalent dimetallic centers of each bis‐dimetallic compound are split, with the splitting — a measure of the electronic coupling — depending on both the metal and bridging ligand. The mixed‐valence species of the dirhodium species was investigated, and the electronic coupling matrix element calculated from the experimental intervalence band parameters for one of them (86 cm –1 ) indicates a significant inter‐component electronic interaction which compares well with good electron conducting anionic bridges such as cyanides. Although none of these compounds is luminescent, the M 2 LCT excited state of one of the bis‐dirhodium complexes is relatively long‐lived (about 6 μs) in degassed acetonitrile at room temperature. The results presented here are promising for the development of linear poly‐dimetallic complexes built on longer naphthyridine‐based strands, with significant long‐range electronic coupling and molecular‐wire‐like behavior. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 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) | 0.000 | 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".