The Redox‐Active Chromium Phthalocyanine System: Isolation of Five Oxidation States from Pc<sup>4−</sup>Cr<sup>I</sup> to Pc<sup>2−</sup>Cr<sup>III</sup>
Bibliographic record
Abstract
Abstract The preparation and structural characterization of a series of chromium phthalocyanine complexes with multiple metal and ring oxidation states were achieved using PcCrII (1) (Pc=phthalocyanine) or PcCrII(THF)2 (1⋅THF2) as starting materials. The reaction of soluble 1⋅THF2 with Br2 or I2 gave the PcCrIII halide complexes PcCrX(THF) (X=I/I3, Br; 3, 4, respectively). Treatment of 1 with 0.5 equivalent of PhIO or air generated the dinuclear [PcCr(THF)]2(μ‐O) (5), whereas the addition of one equivalent of AgSbF6 to 1 resulted in oxidation to THF‐solvated octahedral [PcCrIII(THF)2]SbF6 (6). The reduction of 1 with three sequential equivalents of KEt3BH resulted in the isolation of [K(DME)4][Pc3−CrII] (7), [K(DME)4]2[Pc4−CrII] (8) and [K6(DME)4][Pc4−CrI]2 (9), respectively. The reduced products are deep purple in colour, with visible absorption maxima between 500–580 nm. The ring‐reduced complexes 7 and 8 are monomeric, whereas 9 is a 1D chain of dinuclear [PcCr]2 units with intercalated K+ cations and supported by Cr−Cr interactions of 2.988(2) Å. Addition of four equivalents of KC8 resulted in the demetallated product PcK2(DME)4 (10), which has a 1D chain structure. The isolation and structural characterization of new PcCr complexes spanning five oxidation states, including rare examples of crystalline reduced Pc‐ring species emphasizes the broad redox activity and stability of phthalocyanine‐based complexes.
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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) | 0.001 | 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 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".