Singlet and Triplet Energy Transfers in Tetra-(<i>meso</i>-truxene)zinc(II)- and Tetra-(<i>meso</i>-tritruxene)zinc(II) Porphyrin and Porphyrin-Free Base Dendrimers
Bibliographic record
Abstract
The synthesis, optical properties, and energy transfer features of four dendrimers composed of meso-tetrasubstituted zinc(II) porphyrin (ZnP) or a free base (P) central core, where the substituents are four truxene (Tru) or four tritruxene dendrons (TriTru), TruP, TriTruP, TruZnP, and TriTruZnP, are reported. Selective excitation of the truxene donors results in a photoinduced singlet energy transfer from the truxenes to the porphyrin acceptor. The rates for singlet energy transfer (k(ET)), evaluated from the change in the fluorescence lifetime of the donors (Tru and TriTru) in the presence and absence of the acceptor (P or ZnP) for TruP, TruZnP, TriTruP, and TriTruZnP, are 5.9, 1.2, 0.87, and 0.74 (ns)(-1) at 298 K and 2.6, 2.6, 2.7, and 1.2 (ns)(-1) at 77 K, respectively. A slow triplet-triplet energy transfer from truxene to porphyrin cores in glassy 2MeTHF at 77 K is also reported with rates of 1.3 × 10(3) and 0.10 × 10(2) s(-1) for TruZnP and TriTruZnP, respectively. If the Dexter mechanism for the triplet energy transfers is considered, these slow rates are easily explained by a poor orbital overlap between the truxene and porphyrin π systems. The fluorescence quantum yields (Φ(F)) are 0.20 and 0.16 for TruP and TriTruP and 0.08 and 0.10 for TruZnP and TriTruZnP, respectively at 298 K. At 298 K, a phosphorescence from TruZnP at 795 nm was also observed and is associated with the ZnP chromophore.
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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".