Unexpected Influence of Substituents on the Binding Affinities of Polycyclic Aromatic Hydrocarbons with a Tetra-Au(I) Metallorectangle
Bibliographic record
Abstract
A tetragold supramolecular organometallic cage constructed with two pyrene-bis(imidazolylidene) ligands and two carbazolyl-bis(alkynyl) linkers (1) was studied as a host for a series of substituted polycyclic aromatic hydrocarbons (PAHs). For the two smaller PAHs used (2-naphthalenol and 1-pyrenemethanol), the presence of the −OH groups at the periphery of the molecules did not enhance the binding affinity of the guest, in comparison with the unsubstituted PAHs. This observation indicated no hydrogen bonding of these two guests with the NH of the carbazole linker, as well as negligible dispersive interactions of the substituents with the π system of 1. In the case of 3-perylenemethanol, the CH2OH group produced a significant increase in the binding affinity vs that of perylene. Similarly, 3-methylperylene shows an increased binding affinity in comparison to perylene. MN15-L/def2-QZVP calculations gave Gibbs reaction energies for the displacement of perylene from the host by the substituted perylenes becoming more exergonic in the order −1.6 (3-methylperylene) > −4.3 (3-ethylperylene) > −4.5 kcal/mol (3-perylenemethanol). The experimental and DFT results indicate that the peripheral dispersive interactions can make a significant contribution to the host–guest bonding energy, in addition to the conventional π–π stacking interactions. Our work highlights the importance of dispersive interactions in the contribution to the binding affinity of host–guest chemistry complexes.
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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".