[Pt(SCN)<sub>4</sub>]<sup>2–</sup>‐Based Coordination Polymers and Supramolecular Squares: Intermolecular Pt···H–C Interactions Probed by Luminescence Spectroscopy at Variable Pressure
Bibliographic record
Abstract
The structures of four types of supramolecular systems containing [Pt(SCN)4]2– molecular units have been characterized. [Mn(bipy)2Pt(SCN)4]2·2MeOH (1) and [Zn(bipy)2Pt(SCN)4]2·2MeOH (2) show cis‐thiocyanato ligands bridging the PtII and MnII or ZnII ions, leading to a molecular square motif. [Zn(bipy)2Pt(SCN)4]2 (3) presents chains where trans‐thiocyanato ligands bridge the ZnII and PtII ions. For 1–3, free thiocyanato ligands are coordinated to the PtII centers to complete the square‐planar coordination. [Pb(bipy)2Pt(SCN)4]2 (4) reveals a two‐dimensional sheet structure where all SCN– ligands bridge the PbII and PtII ions. [Pb(terpy)Pt(SCN)4]2 (5) is similar to 3, with two bridging trans‐SCN– ligands and two that are coordinated only to the PtII centers. For all compounds, d–d luminescence is observed with band maxima at approximately 14600 cm–1 (690 nm). Spectra show characteristic shifts with pressure, indicative of either intramolecular or intermolecular effects, depending on the sign of the shift. The pressure‐dependent shifts for 1–5 show rich variations. A well‐documented shift to higher energy due to metal–ligand bond compression is observed for 5 and can be used as a basis for a comparison. Compounds 1–4 show a shift of Emax to lower energy with pressures below 10 kbar. A change in sign for the shift of Emax occurs at 20, 12, and 10 kbar for 1, 2, and 3, respectively. For 4, only a shift to lower energy is observed. Competing intra‐ and intermolecular effects lead to these variations.
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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".