Detailed Geometric and Electronic Structures of a One‐Electron‐Oxidized Ni Salophen Complex and Its Amido Derivatives
Bibliographic record
Abstract
Abstract Square‐planar nickel(II) complexes of 1,2‐bis(2‐hydroxy‐3,5‐di‐ tert ‐butylbenzimino)benzene ([ 1 ]), 1‐(2‐hydroxy‐3,5‐di‐ tert ‐butylbenzimino)‐2‐(2‐hydroxy‐3,5‐di‐ tert ‐butylbenzamido)benzene ([ 2 ] – ) and 1,2‐bis(2‐hydroxy‐3,5‐di‐ tert ‐butylbenzamido)benzene ([ 3 ] 2– ) were chemically oxidized by one‐electron to afford nickel–radical species with non‐negligible metal contribution to the singly occupied molecular orbital (SOMO). The X‐ray crystal structure of [ 1 ][SbF 6 ]shows an almost symmetric metal coordination sphere and phenoxyl pattern within the ligand framework. The spin population at the nickel ion calculated by DFT (B3LYP) does not evolve monotonically within the series, and the values are 18.7, 19.5, and 42.7 % for [ 1 ] + , [ 2 ], and [ 3 ] – , respectively. Complexes [ 1 ] + , [ 2 ], and [ 3 ] – each exhibit a weak near‐IR (NIR) band at 3600, 4440, and 5900 cm –1 , respectively, the origin of which differs. For [ 1 ] + , it corresponds to an intervalence charge transfer (IVCT) transition (β‐HOMO → β‐LUMO) typical for delocalized compounds (calcd. 3700 cm –1 ). For [ 2 ], which is a localized radical, it is assigned to an intraligand charge transfer (CT) transition (calcd. 5000 cm –1 ). Although the CT transition still involves orbitals mainly centered on the ligand, it acquires significant ligand‐to‐metal charge transfer (LMCT) character in the case of [ 3 ] – (calcd. 5700 cm –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 | 0.001 | 0.001 |
| 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 | 0.001 |
| 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 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".