Crystal Lattice-Induced Stress modulates Photoinduced Jahn–Teller Distortion Dynamics
Bibliographic record
Abstract
High Resolution Image Download MS PowerPoint Slide Efficient photoredox chemical transformations are essential to the development of novel, cost-effective, and environmentally friendly synthetic methodologies. The concept of the entatic state in bioinorganic catalysis proposes that a preorganized structural configuration can reduce the energy barriers associated with chemical reactions. This concept provides one of the guiding principles to enhance catalytic efficiency by maintaining high-energy conformations close to the reaction’s transition state. Copper(I)-based photocatalysts, recognized for their low toxicity and highly negative oxidation potentials, are of particular interest in entasis studies. In this study, we explore the impact of entasis caused by stress induced by the surrounding lattice on the excited state dynamics of a prototypical copper(I)-based photocatalyst in a single crystal form. Using femtosecond broadband transient absorption spectroscopy, we show that triplet state formation from the entactic state is faster (∼3.9 ps) in crystals compared with solution (∼11.3 ps). The observed faster intersystem crossing in crystals hints toward the possible existence of distorted square planar geometry with higher spin–orbit coupling at the minima of the S 1 state. We further discuss the influence of entasis on vibrationally coherent photoinduced Jahn–Teller distortions. Our findings reveal the photophysical properties of the copper complex under lattice-induced stress, which can be extended to enhance the broader applicability of the entatic state concept in other transition metal systems. Understanding how environmental stress-induced geometric constraints within crystal lattices affect photochemical behavior opens avenues for designing more efficient photocatalytic systems based on transition metals, potentially enhancing their applicability to sustainable chemical synthesis.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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".