Thermochromic Solid-State Emission of Dipyridyl Sulfoxide Cu(I) Complexes
Bibliographic record
Abstract
Copper(I) complexes ( Cu-DPSO and Cu-Me-DPSO ) utilizing sulfoxide-bridged dipyridyl ligands are reported. Cu-DPSO demonstrates photophysical properties typical with [Cu(disphosphine)(diimine)] + complexes, however with additional steric bulk in the 6- and 6′-positions of the diimine ligand to give complex Cu-Me-DPSO; the photophysics are greatly altered. This species is isolated as an amorphous powder ( a -Cu-Me-DPSO ) which emits yellow light; upon heating to 180 °C, a crystalline powder is formed ( c -Cu-Me-DPSO ) which shows a large bathochromic shift (>100 nm) in emission, and shows orange luminescence attributed to a flattening distortion of the complex away from a tetrahedral geometry. On cooling to −196 °C, c -Cu-Me-DPSO displays a reversible thermochromic solid-state emission, from orange at room temperature to yellow at low temperatures. Using solid-state variable temperature excitation and absorption data, this phenomenon is attributed to a change in coordination geometry about the copper atom in the excited state. At low temperatures, a pseudo-tetrahedral geometry is preferred, giving higher energy emission, whereas, at higher temperatures, a flattened geometry dominates, giving a lower energy emission under UV irradiation. This is a unique example of a monometallic copper(I) complex capable of reversible thermochromic emission in the solid state, and highlights the impact that subtle ligand tuning plays on the photophysical properties. Previous copper(I) thermochromic materials were limited to copper halide clusters, and this study opens new avenues toward highly functionalized, thermal stimuli-responsive materials.
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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".