Solvation Entropy as a Lever for Steering the Macroscopic Properties of a Functional Supramolecular Helical Polymer
Bibliographic record
Abstract
Abstract Solvent‐solute interactions are utterly important in supramolecular polymers (SPs), yet the high responsivity of SPs to solvent polarity makes it challenging to play on other solvation effects to tune their macroscopic properties in a rational manner. Herein, we report the characterization at various scales of the assembly properties of a C 2 ‐symmetric benzene‐1,3,5‐tricarboxamide monomer with two (1 S )‐methylheptyl moieties and one diphenylphosphino group as lateral chains. Our investigation reveals a highly cooperative structural transition between two SP states, which can exquisitely be tuned by solvents of similar polarities, leading to variation of the transition temperature (T*) over a range of 85 K. The structural transition was detected in 4 pure solvents and 13 toluene/cosolvent mixtures; a fair relationship is determined between T* and the solvent molar volume. The transition is only weakly favored by enthalpy (by ca. 2 kJ.mol −1 at 286 K). However, minimization of the entropic cost leads to a notable increase in the T*. This allows a fine tuning of the thermothickening and catalytic properties of the resulting SPs auguring that solvation, and notably solvation entropy, may constitute an important lever for steering SPs structure and 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".