Room Temperature Magnetic Switchability Assisted by Hysteretic Valence Tautomerism in a Layered Two-Dimensional Manganese-Radical Coordination Framework
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Bibliographic record
Abstract
The manganese-nitronyl-nitroxide two-dimensional coordination polymer {[Mn 2 (NITIm) 3 ]ClO 4 } n ( 1 ) (NITImH = 2-(2-imidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1 H -3-oxide-1-oxyl) undergoes an unusual hysteretic thermo-induced valence tautomeric transition near room temperature, during which the manganese(II) ions are oxidized to manganese(III) and two of the three deprotonated radicals (NITIm – ) are reduced to their diamagnetic aminoxyl form (denoted NIT Red 2– ). Upon cooling, the high-temperature species {[Mn II 2 (NITIm) 3 ]ClO 4 } n ( 1 HT ) turns into the low-temperature species {[Mn III 2 (NIT Red ) 2 (NITIm)]ClO 4 } n ( 1 LT ) around 274 K, while on heating the process is reversed at about 287 K. This valence tautomeric phenomenon is supported by temperature-dependent magnetic susceptibility measurements, differential scanning calorimetry (DSC), crystal structure determination, UV–vis absorption, X-ray absorption (XAS), and emission (XES) and electron paramagnetic resonance (EPR) spectroscopies in the solid state.
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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 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 it