Why do the luminescence maxima of isostructural palladium(II) and platinum(II) complexes shift in opposite directions?
Bibliographic record
Abstract
Temperature-dependent luminescence spectra for a series of palladium(II) and platinum(II) complexes with thiocyanate, halide, and dithiocarbamate ligands are presented. All complexes show broad d−d luminescence. Crystal structures are reported for (n-Bu4N)2[Pt(SCN)4] and (n-Bu4N)2[Pd(SCN)4] at 150 and 250 K, for the palladium(II) dimethyldithiocarbamate (MeDTC) complex [Pd(MeDTC)2] at 150 and 300 K, and for its platinum(II) analog at 100 and 300 K. The structures of (n-Bu4N)2[Pt(SCN)4], (n-Bu4N)2[Pd(SCN)4], and [Pt(MeDTC)2] show similar volume increases with temperature. In contrast, the luminescence band maxima of palladium(II) and platinum(II) complexes have opposite shifts with increasing temperature. (n-Bu4N)2[Pd(SCN)4] shows a shift of −2.0 cm−1/K and [Pd(MeDTC)2] a shift of −1.1 cm−1/K, while both platinum(II) complexes have a positive shift of +1.6 cm−1/K. Calculated luminescence spectra with adjustable parameters reproduce the experimental spectra. The variation of their parameters with temperature shows the origin of different trends. Temperature-dependent luminescence spectra of [Pd(SCN)4]2− and [Pt(SCN)4]2− in polymer films of polyvinyl alcohol were measured. No clearcut shifts of maxima were observed for either compound, and their spectra are broader due to the disordered environment.
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.000 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".