Hetero trinuclear oxo-bridged complexes of ruthenium porphyrin and iron phthalocyanine
Bibliographic record
Abstract
New diamagnetic hetero bi- and trinuclear oxo-bridged metal complexes of formula (L)(Pc)Fe-O-Ru(TPP')(O) and (L)(Pc)Fe-O-Ru(TPP')-O-Fe(Pc)(L) have been prepared from Ru(TPP')(O)2 and Fe(Pc)(L)2 (TPP' = tetrakis(4-methoxyphenyl)porphyrinate, Pc = phthalocyanate ion, L = monodentate ligand). The trinuclear complex binds a variety of ligands (4,4'-bipy, 4-MePy, P(OEt)3, pip, NH3, 1-MeIm, P(Me)2Ph) trans to the oxo-bridge. 1H NMR spectra are characterized by large ring current shifts (rcs) due to the TPP' and Pc ions. The complexes show an unusually weak Pc Q band in their visible spectra at 700 nm and two CT bands in the near-IR region from 1000 to 1500 nm, which are sensitive to the trans ligand. The trinuclear complex can be reversibly oxidized to the +1 and +2 ions, formally Fe(IV)-O-Ru(IV)-O-Fe(III) and Fe(IV)-O-Ru(IV)-O-Fe(IV) at 0.4 and 0.76 V. The +1 ion is chemically obtained by reaction of the neutral species with (Cp)2Fe+ for L = 4-MePy and this reaction is reversed upon addition of L' = P(Me)2Ph. Reductive cleavage by hydroquinone, phosphines and phosphites are the slowest of all RuTPP[O(FeN4)]2 systems studied to date (t1/2 = 8 h at 40°C).Key words: ruthenium, iron, porphyrin, phthalocyanine, oxo.
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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".