Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight
Abstract
:1. Introduction
2. Results and Discussion
2.1. The Influence of the Ligand on the Cage
2.1.1. The Ligand Role in the Supramolecular Helicate/Mesocate Isomerism
2.1.2. The Ligand Role on the Cage Structure
2.2. The Influence of the Guest on Cage
2.2.1. The Guest Role in the Supramolecular Isomerism
2.2.2. The Guest’s Role in the Cage Structure
3. Materials and Methods
4. Conclusions
- (i)
- if one is interested in estimating the stability of one isomer with respect to the others, in vacuum calculations are adequate;
- (ii)
- if one is interested in good agreement with geometrical parameters (error on distances <0.5%), the inclusion of solvent and dispersion correction is imperative;
- (iii)
- the accordance with experimental geometrical parameters depends on the flexibility of the ligands: the more flexible the ligand, the larger the average percentage errors.
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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In Vacuum | Solvent | Solvent-D | SCXRD | |
---|---|---|---|---|
NEt4⊂C1 | ||||
Most stable | Helicate | Helicate | Helicate | Helicate |
ΔEH–M | 7.66 | 6.33 | 11.55 | // |
dLa–La | 10.424 (−0.02%) | 10.392 (−0.32%) | 10.465 (0.37%) | 10.426 |
dside | 12.682 (3.63%) | 12.691 (3.70%) | 12.298 (0.49%) | 12.238 |
dopp | 17.936 (3.26%) | 17.919 (3.16%) | 17.390 (0.12%) | 17.370 |
NEt4⊂C3 | ||||
Most stable | Helicate | Helicate | Helicate | Helicate |
ΔEH–M | 8.89 | 5.77 | 6.12 | // |
dLa–La | 11.664 (−3.24%) | 11.610 (−3.68%) | 11.902 (−1.26%) | 12.054 |
dside | 9.266 (3.50%) | 9.295 (3.82%) | 8.952 (−0.01%) | 8.953 |
dopp | 13.120 (3.88%) | 13.142 (4.05%) | 12.647 (0.13%) | 12.630 |
NEt4⊂C8 | ||||
Most stable | Mesocate | Mesocate | Helicate | Mesocate |
ΔEH–M | −0.07 | −1.67 | 1.77 | // |
dLa–La | 11.621 (−1.46%) | 11.570 (−1.91%) | 11.937 (1.20%) | 11.795 |
dside | 9.568 (4.65%) | 9.562 (4.58%) | 9.233 (0.98%) | 9.143 |
dopp | 13.532 (4.66%) | 13.522 (4.58%) | 13.057 (0.98%) | 12.930 |
In Vacuum | Solvent | Solvent-D | |
---|---|---|---|
NEt4⊂C1 | 7.66 | 6.33 | 11.55 |
NEt4⊂C2 | 10.10 | 12.43 | 13.02 |
NEt4⊂C3 | 8.89 | 5.77 | 6.12 |
NEt4⊂C4 | 12.43 | 10.80 | 8.57 |
NEt4⊂C5 | 6.49 | 6.14 | 6.66 |
NEt4⊂C6 | 7.11 | 4.81 | 5.12 |
NEt4⊂C7 | 2.58 | 1.47 | 2.37 |
NEt4⊂C8 | −0.07 | −1.67 | 1.77 |
Empty | NMe4+ | NEt4+ | NPr4+ | NBu4+ | |
---|---|---|---|---|---|
NR4⊂C1 | |||||
Most stable | Helicate | Helicate | Helicate | Helicate | Helicate |
ΔEH–M | 2.68 | 6.07 | 6.33 | 3.37 | 5.72 |
dLa–La | 10.130 (10.616) | 10.253 (10.465) | 10.392 (10.552) | 10.597 (10.884) | 10.564 (10.832) |
dside | 12.736 (12.435) | 12.672 (12.570) | 12.671 (12.558) | 12.565 (12.435) | 12.663 (12.524) |
dopp | 18.010 (17.589) | 17.943 (17.777) | 17.912 (17.759) | 17.767 (17.580) | 17.907 (17.709) |
Aeq | 162 (155) | 161 (158) | 161 (158) | 158 (155) | 160 (157) |
Vinner | 548 (547) | 549 (551) | 556 (555) | 557 (561) | 565 (566) |
NR4⊂C8 | |||||
Most stable | Helicate | Helicate | Mesocate | Mesocate | Mesocate |
ΔEH–M | 3.29 | 0.50 | −1.67 | −0.79 | // a |
dLa–La | 12.187 (12.197) | 11.651 (11.682) | 11.421 (11.570) | 11.208 (11.232) | (10.949) |
dside | 9.133 (9.099) | 9.520 (9.492) | 9.657 (9.562) | 9.779 (9.784) | (9.988) |
dopp | 12.917 (12.868) | 13.467 (13.424) | 13.658 (13.522) | 13.856 (13.834) | (14.125) |
Aeq | 83 (83) | 91 (90) | 93 (91) | 96 (96) | (100) |
Vinner | 337 (337) | 352 (351) | 355 (353) | 357 (358) | (364) |
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Carlotto, S.; Armelao, L.; Rancan, M. Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight. Int. J. Mol. Sci. 2022, 23, 10619. https://doi.org/10.3390/ijms231810619
Carlotto S, Armelao L, Rancan M. Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight. International Journal of Molecular Sciences. 2022; 23(18):10619. https://doi.org/10.3390/ijms231810619
Chicago/Turabian StyleCarlotto, Silvia, Lidia Armelao, and Marzio Rancan. 2022. "Helicate versus Mesocate in Quadruple-Stranded Lanthanide Cages: A Computational Insight" International Journal of Molecular Sciences 23, no. 18: 10619. https://doi.org/10.3390/ijms231810619