Ultrafast Electron Transfers in Organometallic Supramolecular Assemblies Built with a NIR-Fluorescent Tetrabenzoporphyrine Dye and the Unsaturated Cluster Pd<sub>3</sub>(dppm)<sub>3</sub>(CO)<sup>2+</sup>
Bibliographic record
Abstract
The sodium 9,18,27,36-tetra-(4-carboxyphenylethynyl)tetrabenzoporphyrinatozinc(II) ( TCPEBP ) and sodium 5,10,15,20-tetra-(4-carboxyphenylethynyl)porphyrinatozinc(II) ( TCPEP, for comparison purposes) salts were prepared to investigate the ionic driven host–guest assemblies made with the unsaturated redox-active cluster Pd 3 (dppm) 3 (CO) 2+ ( [Pd 3 2+ ], dppm = Ph 2 PCH 2 PPh 2 as a PF 6 – salt). Nonemissive dye··· [Pd 3 2+ ] x assemblies ( x = 1–4) are formed in methanol with K 1 x (binding constants) values of 83 200 ( TCPEBP ) and 70 400 M –1 ( TCPEP; average values extracted from graphical methods (Benesi–Hildebrand, Scott, and Scatchard), matching those obtained from fluorescence quenching experiments (static model)). These values are consistent with the more electron rich TCPEBP dye. This conclusion is corroborated by electrochemical data, which indicate a lower oxidation potential of the TCPEBP dye (+0.46 V) vs TCPEP (+0.70 V vs SCE) and by shorter calculated average Pd···O distances (DFT (B3LYP): 3.259 vs 3.438 Å, respectively). Using the position of the 0–0 component of the Q-bands and the electrochemical data, the excited-state driving forces for dye*··· [Pd 3 2+ ] x → dye +• ··· [Pd 3 +• ][Pd 3 2+ ] x –1 are estimated for TCPEBP (+1.22 V vs SCE) and TCPEP (1.08 V vs SCE). The time scale for this process occurs within the laser pulse (fwhm <75–110 fs) during the measurements of the femtosecond transient absorption spectra. Conversely, the back electron transfers (dye +• ··· [Pd 3 +• ][Pd 3 2+ ] x –1 → dye··· [Pd 3 2+ ] x ) occur well within 1 ps (respectively 650 and 170 fs for TCPEBP and TCPEP ). Arguments are provided that the reorganization energy governs this difference.
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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".