Platinum(II) Complexes with Pyridyl Azolate-Based Chelates: Synthesis, Structural Characterization, and Tuning of Photo- and Electrophosphorescence
Bibliographic record
Abstract
A new series of luminescent platinum(II) azolate complexes with a formula of [Pt(NwedgeN)(2)], in which NwedgeN = mppz (1), bppz (2a), bzpz (2b), bmpz (2c), bqpz (2d), fppz (3a), hppz (3b), bptz (4), hptz (5), were synthesized, and their photophyscial properties were examined. Single-crystal X-ray diffraction studies of 2c and 3b revealed a planar molecular geometry, in which the NwedgeN chelates adopt a trans configuration and show notable interligand C-H...N hydrogen bonding within the complex. Interesting intermolecular interactions were observed in the solid state. Complex 2c formed a slipped-stack structure with a Pt...Pt separation distance of 6.432 Angstroms, while complex 3b showed a columnar stacking with the molecules oriented in an alternating order in relation to the chain axis, giving a much reduced Pt...Pt distance of 3.442 Angstroms. The lowest absorption band for all complexes revealed strong state mixings between the singlet and triplet (MLCT and intraligand pipi) manifolds. Complexes 1 and 2 showed mixed (3)MLCT and (3)pipi phosphorescence in fluid solution. While radiationless deactivation was apparently dominant for complexes 3-5 in solution, resulting in rather weak emission, strong phosphorescence was observed in the room-temperature solid state with the peak wavelength being significantly red shifted compared to that in solution. The emission nature has been tentatively assigned to be (3)MMLCT in character. OLED devices with a multilayer configuration of ITO/NPB/CBP:2a/BCP/Alq(3)/LiF/Al were successfully fabricated using a CBP layer doped with various amount of 2a, ranging from 6 to 100%, as the emitting layer. A substantial red shift with increasing doping concentrations was observed in electroluminescence. With a neat film of 2a, the device showed a green emission with lambda(max) at 556 nm and an external QE of approximately 1.6% at a driving current of 20 mA. Similarly, for the device using a neat film of 3a, an electroluminescence centered at 616 nm with a slightly reduced external QE of approximately 2.1% was recorded. Aggregation of platinum(II) complexes in the solid state was proposed to account for the large red-shift in electroluminescence.
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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) | 0.000 | 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".