Thermally-induced hysteretic valence tautomeric conversions in the solid state <i>via</i> two-step labile electron transfers in manganese-nitronyl nitroxide 2D-frameworks
Bibliographic record
Abstract
Near room temperature hysteretic thermo-induced valence tautomerism was discovered in a layered 2D-coordination polymer of manganese(ii) with nitronyl nitroxide radicals separated by ClO4- anions (1). This opens a novel approach towards switchable materials with hysteresis and under ambient conditions with prospects for applications and for investigating solid-state intramolecular electron transfers. Herein, two new compounds with similar layered structures where the anions (X) are BF4- (2) or PF6- (3) are presented. Their magnetic behaviors also reveal hysteretic thermo-induced valence tautomeric conversions but in two steps and evidencing a strong effect of the anion. This occurs near room temperature (278-220 K) for 2 and higher for 3 (380-330 K). Their single crystal structures at different temperatures show that this involves two successive thermally-triggered electron transfers with switching between three redox tautomers formulated as {[MnII2-yMnIIIy(NITIm)3-y(NITRed)y]X}n, where y is temperature dependent. Upon cooling from the high-temperature redox-tautomer (y = 0) to the intermediate one (y = 1), half of the manganese(ii) centers are oxidized to manganese(iii) and 1/3 of the nitronyl nitroxide radicals (NITIm-) are reduced to the aminoxyl form (NITRed2-). On further cooling, the second half of the manganese(ii) centers are oxidized and another 1/3 of the radicals are reduced to reach the low-temperature redox-tautomer (y = 2). Upon reheating, reverse electron transfers occur. This is complementarily supported by X-ray powder measurements, differential scanning calorimetry, and electron paramagnetic resonance and Raman spectroscopies. These multi-stable compounds in which manganese ions exchange reversibly their electron with the nitronyl nitroxide radical are outstanding rare examples of two-step valence tautomerism in the solid state promoted by the polymeric structure.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 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) | 0.001 | 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 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".