Bibliographic record
Abstract
High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study two complexes of high-spin manganese(III), d(4), S = 2. The complexes studied were (tetraphenylporphyrinato)manganese(III) chloride and (phthalocyanato)manganese(III) chloride. Our previous HFEPR study (Goldberg, D. P.; Telser, J.; Krzystek, J.; Montalban, A. G.; Brunel, L.-C.; Barrett, A. G. M.; Hoffman, B. M. J. Am. Chem. Soc. 1997, 119, 8722-8723) included results on the porphyrin complex; however, we were unable to obtain true powder pattern HFEPR spectra, as the crystallites oriented in the intense external magnetic field. In this work we are now able to immobilize the powder, either in an n-eicosane mull or KBr pellet and obtain true powder pattern spectra. These spectra have been fully analyzed using spectral simulation software, and a complete set of spin Hamiltonian parameters has been determined for each complex. Both complexes are rigorously axial systems, with relatively low magnitude zero-field splitting: D approximately -2.3 cm(-)(1) and g values quite close to 2.00. Prior to this work, no experimental nor theoretical data exist for the metal-based electronic energy levels in Mn(III) complexes of porphyrinic ligands. This lack of information is in contrast to other transition metal complexes and is likely due to the dominance of ligand-based transitions in the absorption spectra of Mn(III) complexes of this type. We have therefore made use of theoretical values for the electronic energy levels of (phthalocyanato)copper(II), which electronically resembles these Mn(III) complexes. This analogy works surprisingly well in terms of the agreement between the calculated and experimentally determined EPR parameters. These results show a significant mixing of the triplet (S = 1) excited state with the quintet (S = 2) ground state in Mn(III) complexes with porphyrinic ligands. This is in agreement with the experimental observation of lower spin ground states in other metalloporphyrinic complexes, such as those of Fe(II) with S = 1.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".