Cyclic Azobenzene-Containing Side-Chain Liquid Crystalline Polymers: Synthesis and Topological Effect on Mesophase Transition, Order, and Photoinduced Birefringence
Bibliographic record
Abstract
A cyclic side-chain liquid crystalline polymer (SCLCP) bearing azobenzene mesogens, namely, poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate} (PAzoMA), was successfully synthesized by using “click” cyclization of the linear polymer precursor with alkyne and azide end groups. Samples of cyclic-PAzoMA of various molecular weights were prepared, characterized, and studied in comparison with their linear counterparts. The results show that the topological constraint arising from the tortuosity of the ring structure and the absence of chain ends in cyclic-SCLCPs affects profoundly the liquid crystalline (LC) phase transitions (temperature, enthalpy, and entropy) of mesogenic side groups and that this topological effect is more prominent for smaller SCLCP rings. Moreover, the photoinduced anisotropy in films as a result of the trans−cis photoisomerization of azobenzene mesogens was investigated, and cyclic-PAzoMA was found to behave differently from linear-PAzoMA. On the one hand, the cyclic polymer exhibits a nonmonotonic rise and erasure of birefringence upon linearly and circularly polarized excitation (488 nm), respectively, in contrast with the linear polymer displaying monotonic changes. On the other hand, unlike the linear polymer, the photoinduced orientation of azobenzene mesogens in cyclic-PAzoMA cannot be enhanced upon annealing in the nematic phase. All these manifestations of the topological constraint suggest that cyclization offers a new way to change the coupling between mesogenic side groups and chain backbone of SCLCPs, and their interplay under the additional topological effect may generate new behaviors that are of interest to be explored.
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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) | 0.000 | 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 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".