H-Bonding Control of Supramolecular Ordering of Diketopyrrolopyrroles
Bibliographic record
Abstract
Diketopyrrolopyrrole (DPP) is a widely used building block for high-mobility ambipolar semiconductors. Hydrogen bonding of N-unsubstituted DPPs has recently been identified as a tool for controlling their solid state structure and properties of semiconducting films, yet little is known about supramolecular packing of H-bonded DPP derivatives. Here we report a comparative study of three archetypical DPP derivatives, difurylDPP (DFDPP), diphenylDPP (DPDPP), and dithienylDPP (DTDPP), at the interface and in bulk crystals. Using scanning tunneling microscopy (STM) combined with X-ray crystallographic analysis, we demonstrate how the interactions of the (hetero)aromatic substituents interplay with H-bonding, causing dramatic differences in the supramolecular ordering of these structurally similar building blocks. Under all explored conditions, DPDPP exclusively forms H-bonded homoassemblies; DFDPP strongly prefers to co-assemble with alkanoic acids, through a rare lactam···carboxylic acid H-bonded complex, and DTDPP, depending on conditions, either co-assembles with alkanoic acids or self-assembles in one of two H-bonded polymorphs. One of these polymorphs suggests an out-of-plane twist of thiophene rings that form π-stacks running along the surface plane; this is unexpected considering the large energetic penalty of DTDPP deplanarization. The results are explained in terms of inter- versus intramolecular interactions, which are quantified with density functional theory calculations. This work shows that aryl substituents can strongly influence H-bonding assembly of DPP derivatives that is likely to affect their charge-transport properties.
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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 | 0.000 |
| 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".