A Versatile Strategy toward Donor–Acceptor Nanofibers with Tunable Length/Composition and Enhanced Photocatalytic Activity
Bibliographic record
Abstract
Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of π-conjugated polymers (CPNFs) in a controlled fashion. However, reports of donor–acceptor (D–A) heterojunction CPNFs are extremely rare. The preparation of these materials remains a challenge due to the lack of rational design guidelines for the D–A π-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D–A- co -oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[ b, d ]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo( p -phenylene ethynylene) heptamer [BT-OPE 7 -BT, FSO-OPE 7 -FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A–D–A π-conjugated structure. In contrast, D–A–D structures with a single BT in the middle of a string of OPE units disrupt the packing. We employed oligomers with a terminal alkyne to synthesize diblock copolymers BT-OPE 7 -BT- b -P2VP and BT-OPE 7 -BT- b -PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly( N -isopropylacrylamide)) and FSO-OPE 7 -FSO- b -P2VP and FSO-OPE 7 -FSO- b -PNIPAM. CDSA experiments with these copolymers in ethanol were able to generate CPNFs of controlled length by both self-seeding and seeded growth as well as block comicelles with precisely tunable length and composition. Furthermore, the D–A CPNFs with a BT-OPE 7 -BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to N -benzylidenebenzylamine. Given the scope of the oligomer compositions examined and the range of structures formed, we believe that the living CDSA strategy with D–A-based co-oligomers opens future opportunities for the creation of D–A CPNFs with programmable architectures as well as diverse functionalities and applications.
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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".