Luminescent Organometallic Complexes Built upon the Nonemissive Azophenine
Bibliographic record
Abstract
Azophenine, C 6 H 2 (═NPh) 2 (NHPh) 2, is renowned to be nonemissive in solution or in the solid state at 298 and 77 K. It was rendered luminescent in solution at room temperature without using any cyclization strategy of the N ∧ N end by anchoring two or four trans -RC≡CPt(PBu 3 ) 2 (C≡C) units (R = hexa- n -hexyltruxene ( Tru )) on the azophenine. Complexes of the general formulas C 6 H 2 (═NC 6 H 4 C≡CSiMe 3 ) 2 (NH PtTru ) 2 ( DiPtTruQ ) and C 6 H 2 (═N PtTru ) 2 (NH PtTru ) 2 ( TertPtTruQ ), where Pt = trans -C 6 H 4 C≡CPt(PBu 3 ) 2 C≡C, exhibit fluorescence (420 nm) and phosphorescence (512 nm) bands arising from upper localized ππ*/C 6 H 4 C≡C to Tru C≡C charge transfer singlet and triplet excited states in 2MeTHF at 298 and 77 K. This latter assignment is based on DFT computations (B3LYP). Moreover, DiPtTru and TertPtTru exhibit low-energy absorption bands with maxima in the 470–485 nm range extending all the way to 600–650 nm. These spectral features are associated with charge transfer (CT) excited states: namely, TruPt → Q ( Q = C 6 H 2 N 2 (NH) 2 ). No emission band (fluorescence or phosphorescence) associated with these CT states has been detected at 298 K, but weak fluorescence bands (λ max ∼750 nm) decaying on the picosecond time scale have been observed in both cases. Biexponential decays were also often noted and likely reflect the presence of the possible conformers associated with the two possible dihedral angles made by the C 6 H 4 plane and the central C 6 H 2 N 2 (NH) 2 core. No evidence for electron transfer between the TruPt arms and Q was observed.
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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".