One-electron reduction of the γ*-isomer of [S<sub>2</sub>W<sub>18</sub>O<sub>62</sub>]<sup>4</sup> leads to isolation of the α-isomer
Bibliographic record
Abstract
Bu4N+ salts of [S2W18O62]5 and [S2W18O62]6 can be isolated by electro reduction of γ*-(Bu4N)4[S2W18O62] in MeCN. α-(Bu4N)5[S2W18O62]·4MeCN crystallizes in space group C2/c with a = 26.226(2) Å, b = 15.570(2) Å, c = 38.407(2) Å, β = 115.59(2)°, V = 14 145(2) Å3, and Z = 8. The observations indicate that a γ* « α isomerization is associated with the [S2W18O62]4 [S2W18O62]5 couple. However, the transformation could not be detected on the timescale of cyclic voltammetry up to a scan rate of 10 V s1. The available data suggest that either: (i) the γ* « α equilibrium favors one of the isomers in solution for both redox states, or (ii) the isomerization is slow on the cyclic voltammetric timescale but the differences in E1/2 values for the α-[S2W18O62]4[S2W18O62]5 and γ*-[S2W18O62]4[S2W18O62]5 couples cannot be resolved by cyclic voltammetry.Key words: polyoxometalates, synthesis, electrochemistry, isomerization.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".