Harnessing Direct (Hetero)Arylation in Pursuit of a Saddle-Shaped Perylene Diimide Tetramer
Bibliographic record
Abstract
This contribution explores the direct (hetero)arylation (DHA) cross-coupling of a saddle-like, π-conjugated cyclooctatetrathiophene (Th4) core with the N-annulated perylene diimide (PDI) chromophore. Replacing the bulky pivalic acid with acetic acid enabled a facile cross-coupling, selectively forming a PDI tetramer (Th4PDI4) in a 70% overall yield. The optoelectronic properties of Th4PDI4 were characterized and density functional theory (DFT) was used to calculate the optimized molecular geometry and molecular orbitals (MOs). Energy levels of MOs determined by cyclic voltammetry corresponded well with those calculated using DFT. The molecular geometry calculated by DFT showed Th4PDI4 adopts two separate PDI–PDI conformations (propeller and double-decker). Organic photovoltaic (OPV) devices were fabricated using a blend of PTB7-Th/Th4PDI4, where an initial power conversion efficiency (PCE) of 1.89% was improved by testing a series of solvent additives and thermal annealing techniques. Through use of 3% (v/v) 1-chloronaphthalene additive, a combination of higher short circuit current (Jsc = 10.2 mA/cm2) and fill factor (FF = 42%) led to an overall increase in PCE to 4.26%.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.000 |
| 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 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".