Liquid Crystallinity and Other Properties in Complexes of Cationic Azo-Containing Surfactomesogens with Poly(styrenesulfonate)
Bibliographic record
Abstract
A series of stoichiometric ionically bonded side-chain polymer complexes, constructed from poly(styrenesulfonate) (PSS) and quaternary ammonium-functionalized azo-containing surfactomesogens (SMs) with hexyl and decyl spacers, were prepared under rigorous conditions and thoroughly dried, and their potential thermotropic liquid crystal (LC) properties were investigated. The SM series consists of eight differently substituted azobenzene cores with a range of polarities. In their Br-neutralized form, they are generally crystalline to high temperatures (those with an ethylamine linking group having very slow recrystallization kinetics). Only some of the complexes showed LC properties in unannealed form, while several others required exceedingly long annealing times at appropriate temperatures to reveal LC character, attributed to the semirigid PS backbone, relatively high molecular weight, and strong ionic interactions that greatly retard the kinetics of chain reorganization toward equilibrium. Among the decyl-spacer complexes, only the two with an ethylamine linking group appear intrinsically isotropic, whereas, among the hexyl-spacer complexes, just two revealed LC character. X-ray diffraction (XRD) indicated that the LC structure is generally of an effectively single-layer SmA type, but while the complexes based on SMs with nonpolar tails produce a classical SmA XRD pattern, those with polar tails produce one with a quasi-extinct or reduced intensity first-order diffraction peak. The former also have lamellar thicknesses that are ca. 5 Å less than the latter, in agreement with literature data for all-covalent polystyrene-based analogues and explained by greater mesogen interdigitation for those with nonpolar tails that thus lie in the alkyl spacer subplane. A model proposed to rationalize the apparent extinction of the first-order XRD peak relies on dipole−dipole interactions between the polar mesogens and the ion pairs that allow them to share the same subplane, thus halving the effective lamellar thickness. A study of photoinduced birefringence (PIB) in selected complexes, compared with a spacer-free complex, shows that the flexible spacer plays a significant role in reducing PIB stability.
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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".