Ground- and Excited-State Dynamics of Aluminum and Gallium Corroles
Bibliographic record
Abstract
The steady-state absorption and emission spectra and the temporal fluorescence decay profiles of two metallocorroles, Al(tpfc)(py)(n) and Ga(tpfc)(py)(n) (n = 1,2), have been measured in a noncoordinating solvent, benzene, in a coordinating solvent, pyridine, and in mixed benzene-pyridine solutions. The ground-state spectra reveal that an equilibrium between the pentacoordinate corrole (n = 1) and the hexacoordinate corrole (n = 2) is established in the mixed benzene-pyridine solutions. The ground-state equilibrium constants are 135 M(-1) and 1.0 M(-1) at 295 K for the Al and Ga species, respectively. The excited-state radiative and nonradiative decay constants of the pentacoordinate and the hexacoordinate species have been obtained from measurements of the fluorescence quantum yields and monoexponential fluorescence decay times in pure benzene and pure pyridine. Temporal fluorescence decays of the gallium system in a mixed benzene-pyridine solution are biexponential due to dissociation of the hexacoordinate species in the excited state leading to the establishment of a dissociation-association equilibrium. The rate constants for the pyridine association and dissociation processes for the gallium corrole in the excited state have been measured, k(a)* = 2.3 x 10(8) M(-1) s(-1) and k(d)* = 2.9 x 10(8) s(-1), respectively, leading to a value for the excited-state association equilibrium constant of K(a)* = 0.78 M(-1).
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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) | 0.002 | 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".