Molecular Structures and Redox Properties of Homoleptic Aluminum(III) Complexes with Azobisphenolate (azp) Ligands
Bibliographic record
Abstract
To elucidate the oxidation behavior of the 2,2′-azobisphenolate (azp) ligand, a series of homoleptic 1:2 AlIII complexes of four azp derivatives (L1) with 5,5′-dichloro-, 5,5′-dimethyl-, 5,5′-di-t-butyl-, 3,3′,5,5′-tetramethyl-substituents and of one imino derivative (L2) were synthesized and obtained as TPP[Al(L)2]·solvent (TPP = tetraphenylphosphonium ion). The X-ray crystal structure analyses showed that the two ONO-tridentate ligands were meridionally coordinated to a central AlIII ion in an almost perpendicular manner to give a homoleptic octahedral coordination structure in all the AlIII complexes. The proton nuclear magnetic resonance spectra suggested that all the AlIII complexes retained the homoleptic coordination structure in solution. From the cyclic voltammetry measurements in dichloromethane solutions, all the AlIII complexes with the azp ligands showed two partially reversible oxidation waves, and an additional reversible or partially reversible reduction wave. The substitution effects on the first oxidation and reduction peak potentials were revealed in the AlIII complexes with the azp ligands. On the other hand, the imino complex showed a partially reversible oxidation wave accompanying a film deposition. The density functional theory (DFT) calculations indicated that the molecular orbital (MO) coefficients of the frontier MOs in the AlIII complexes were present on the ligands and were absent on the AlIII ion. These results confirmed that the azp ligands are susceptible to oxidation and can give a relatively stable oxidation species depending upon substituent effects.
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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 | 0.000 | 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 | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.001 |
| 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".