Cross Conjugated Organometallic Polymers Exhibiting Ultrafast Excitation Energy Channeling: Drastic Effect of the Connectivity
Bibliographic record
Abstract
Abstract A polymer composed of 2,6‐diethynylanthraquinone diimine ( AQI ) and trans ‐bis(tributylphosphine)platinum(II), [Pt] , flanked by one tetraphenylpalladium(II)porphyrin (TPPPd) and one para ‐nitrobenzene (C 6 H 4 NO 2 ) is prepared ( P1 : M n = 57000, M w = 124500, Đ = 2.18, DP = 52.5) and is studied by time‐resolved emission spectroscopy and fs transient absorption spectroscopy (fs‐TAS). A model polymer ( AQI (C 6 H 4 NO 2 ) 2 ‐ [Pt] ) n is used for comparison ( P2 : M n = 88200, M w = 188700, Đ = 2.14, DP = 111). Taking advantage of the dynamics of the excited states of [Pt] and TPPPd and those obtained for P1 and P2 , it is shown that the excitation energy absorbed by the central polymer chain, ( AQI‐[Pt] ) n , channels this energy very efficiently, to the pendent TPPPd with a rate of energy transfer, k ET (S 1 ), larger than 2.3 × 10 10 s −1 for an energy transfer 1 ( AQI‐[Pt] )* → TPPPd for P1 at 298 K based on the decrease of the fluorescence lifetime of the ( AQI‐[Pt] ) n chain in P1 compared to P2 . This rate is more accurately estimated by fs‐TAS and is found to be 1.8 × 10 11 s −1 . This rate is ultrafast and is due to a large contribution of the Dexter mechanism across the imine bridge (CN).
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How this classification was reachedexpand
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 | 0.001 |
| 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 teacher head, 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".