Manganese(III) phthalocyanine triflate complexes: Synthesis, structural characterization and axial ligand displacement
Bibliographic record
Abstract
A series of PcMn(III) complexes (Pc [Formula: see text] phthalocyanine) was synthesized and structurally characterized by stripping the chloride from PcMnCl with AgSbF 6 in ortho-dichlorobenzene (DCB) in the presence of DMSO or DMF; this yielded crystals of [PcMn(H[Formula: see text]O)[Formula: see text]]SbF[Formula: see text]⋅2DMSO and [PcMn(H[Formula: see text]O)[Formula: see text]]SbF[Formula: see text]⋅4DMF, respectively, which are insoluble in DCB. The use of AgOSO 2 CF 3 (AgOTf), under similar conditions, yielded DCB-soluble PcMn(DMSO)OTf and PcMn(DMF)OTf, which were structurally characterized. Reacting PcMnCl with AgOTf in DCB, followed by addition of [[Formula: see text]Bu 4 N]OTf generated [Formula: see text]Bu[Formula: see text]N[PcMn(OTf)[Formula: see text]], which is air-stable and soluble in halogenated solvents; structural characterization revealed a six-coordinate Mn(III) “ate” complex with two trans-axially bound triflate anions. The PcMn(III) complexes are green in colour, with Q-band absorptions spanning from 722–739 nm and LMCT bands from 515–547 nm. Addition of neutral donors (THF, OPPh 3 , pyridine, DMSO, DMF) to [Formula: see text]Bu[Formula: see text]N[PcMn(OTf)[Formula: see text]] generated Q-band and LMCT peak shifts consistent with triflate substitution. These results show the utility of axially-bound triflate anions to increase PcM solubility, while still maintaining sufficient lability to permit reactivity at the axial site.
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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 | 0.001 | 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".