Why do the luminescence maxima of isostructural palladium(II) and platinum(II) complexes shift in opposite directions?
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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-Bu 4 N) 2 [Pt(SCN) 4 ] and (n-Bu 4 N) 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-Bu 4 N) 2 [Pt(SCN) 4 ], (n-Bu 4 N) 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-Bu 4 N) 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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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 | 0.000 | 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 it