General rules for the design of molecular photoswitches based on electrocyclization
Bibliographic record
Abstract
Molecular photoswitches undergo a structural transformation upon excitation with light to intraconvert between two or more stable forms. In some cases, the structural rearrangement involves a cyclization reaction, that is, the transition between ring-open and ring-closed molecular forms. In this work we develop simple guidelines for the design of organic molecules able to undergo photochemical electrocyclization, using electronic structure calculations on one of the most widely-used family of molecules in the field, dithienylethene (DTE)-based compounds. We conclude that the ability to photocyclize can be predicted from the localization and symmetry of frontier molecular orbitals. These ideas are based on the Woodward- Hoffmann rules, but go beyond them, allowing the behavior of a more general family of chromophores, chemically substituted DTEs, to be understood. Moreover, our rules have been validated by assessment of a large number of molecular photoswitches that have been previously investigated experimentally. We have also explored the relationship between thermal stability of the closed form and aromaticity. We use the DTE scaffold as the workhorse model in our computational study, however, these simple yet powerful guidelines are expected to be generally valid to guide the design of other diarylethenes.
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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 | 0.000 | 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) | 0.000 | 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".