Metal Dependence on the Bidirectionality and Reversibility of the Singlet Energy Transfer in Artificial Special Pair-Containing Dyads
Bibliographic record
Abstract
The demetalation of a precursor dyad, 3, built upon a zinc(II)-containing artificial special pair and free-base antenna, leads to a new dyad, 4, for singlet energy transfer composed of cofacial free-base porphyrins (acceptor), [Fb] 2 bridged by a 1,4-C 6 H 4 group to a free-base antenna (donor), [Fb] . This dyad exhibits the general structure [M] 2 -C 6 H 4 - [Fb], where [M] 2 = [Fb] 2, and completes a series reported earlier, where [M] 2 = [Mg] 2 ( 2 ) and [Zn] 2 ( 3 ). The latter dyads exhibit a bidirectional energy-transfer process at 298 K for 2 and at 77 K for 3 . Interestingly, a very scarce case of cycling process is observed for the zinc-containing dyad at 298 K. The newly reported compound 4 exhibits a quasi unidirectional process [Fb] *→ [Fb] 2 (major, k ET = 2 × 10 11 s –1 at 298 K), where the remaining is [Fb] 2 *→ [Fb] (minor, k ET = 8 × 10 9 s –1 at 298 K), thus completing all possibilities. The results are analyzed in terms of molecular orbital couplings (density functional theory computations), Förster resonance energy transfer parameters, and temperature dependence of the decay traces. This study brings major insights about artificial special pair-containing dyads and clearly contributes to a better understanding of the communication between the two main components of our models and those already described in the literature.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| 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 teacher head, 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".