Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes
Bibliographic record
Abstract
Luminescence spectra are reported for trans-[MoOCl(CN-t-Bu)(4)]BPh(4) and trans-[MoOF(pyridine)(4)]BPh(4). The maxima of the broad luminescence bands are at energies of 12000 and 13000 cm(-1), respectively. Resolved vibronic structure involves the metal-oxo stretching mode with a vibrational frequency of approximately 950 cm(-1) (Raman) in both compounds. The pressure behavior of the luminescence bands shows a distinct difference: a blue shift of +12 cm(-1) kbar(-1) is observed for [MoOCl(CN-t-Bu)(4)]BPh(4), and a red-shift of -8 cm(-1) kbar(-1) is obtained for [MoOF(pyridine)(4)]BPh(4). At pressures above 25 kbar, the luminescence maximum of [MoOCl(CN-t-Bu)(4)]BPh(4) shows a change from a blue-shift to a red-shift and the Raman peak corresponding to the metal-oxo stretching mode at 954 cm(-1) becomes broad and its maximum decreases with increasing pressure, leading to a strong deviation from the linear increase of +0.24 cm(-1) kbar(-1) observed at pressures below 25 kbar. These unusual pressure effects are rationalized in terms of the influence of pressure on the metal-ligand bonds and oxo-metal-ligand angles using DFT calculations.
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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".