Intermolecular Interactions in Crystals Modulate Intramolecular Excited State Proton Transfer Reactions
Bibliographic record
Abstract
Proton transfer is a fundamental process underlying chemical and biological phenomena, and its dynamics are significantly influenced by the surrounding environment. This paper studies the excited state intramolecular proton transfer (ESIPT) process, which is crucial to the photostability of hydroxyanthraquinone-based pigments through efficient energy dissipation, by investigating how crystalline packing influences photoinduced proton transfer dynamics in single crystals of dihydroxyanthraquinone (DHAQ) constitutional isomers. Comparing the proton transfer dynamics in crystalline and solution phases, we show substantial differences due to the crystalline environment, particularly in the 1,4- and 1,5-DHAQ isomers. These isomers show intermolecular hydrogen bonding within the crystal lattice, resulting in larger excitonic couplings, which significantly alters their reaction pathways compared to their behavior in solution. We show that 1,8-DHAQ, which does not form intermolecular hydrogen bonds in the crystal, shows minimal changes in dynamics between the phases. In contrast, in the case of 1,4-DHAQ, intermolecular interactions within the molecular crystal phase open up an ESIPT relaxation channel, which is not observed in the solution phase. These findings highlight the critical role of crystal packing in modulating proton transfer dynamics and offer insights into how molecular packing can be strategically manipulated to control and optimize reaction pathways in solid-state environments.
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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".