Thio-modified trianglimines, a novel group of chiral macrocyclic compounds of high structural dynamics
Bibliographic record
Abstract
Abstract The embellishing of the macrocycle core with sulfur substituents of varied sterical requirements changes the structural dynamics of chiral, triangular polyimines. Despite their formal high symmetry, these compounds adopt diverse conformations, in which the macrocycle core represents a non-changeable unit. DFT calculations reveal that the mutual arrangement of sulfur-containing substituents is controlled mainly by sterical interactions. The presence of sulfur atoms affects the chiroptical properties of these compounds and causes a red shift of respective absorption bands compared to the basic trianglimine. Unexpectedly, the aromatic fragments attached to the sulfur atom have less impact on ECD spectra, visible only in particular spectral regions. Such a possibility to adapt various conformations is also seen in the crystalline phase; however, a stiff basic unit – the triangular macrocycle core – caused macrocycles’ self-assembly into columnar-like aggregates. In the crystal lattice, around the macrocycle having bulky SCPh 3 groups, a space filled with solvent is formed; however, the macrocycle’s internal cavity is closed and unavailable for guest molecules. Titration of the solutions of basic SBn-substituted imine and amine macrocycles by AgOTf results in significant changes in the ECD spectra, confirming possible binding interactions between macrocycle and metal cations.
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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 | 0.001 |
| 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".