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Thiapillar[5]arenes: Structures, Properties, and Host-Guest chemistry.
- Source :
-
Chemical Physics . May2024, Vol. 581, pN.PAG-N.PAG. 1p. - Publication Year :
- 2024
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Abstract
- [Display omitted] • The lowest-energy conformations of thiapillar[5]arenes are obtained by DFT calculations. • Electronic structure analysis reveals the evolution from electronegativity to electropositivity in the molecular cavities of thiapillar[5]arenes. • Thiapillar[5]arenes are able to accommodate various guests based on the electronic complementarity and the spatial matching. • The sulfur-containing derivatizations of pillar[ n ]arenes are expected to expand the application prospects in supramolecular biology and electrochemistry related fields. The chemical modification of bridging groups of the pillar[ n ]arenes is an important way to functional derivatization and expand the application fields. So far, however, there have been few reports on this issue. On the basis of experimental reports, a series of thiapillar[5]arene structures with sulfur, sulfoxide and sulfone as bridging groups are proposed in this work. By using density functional theory (DFT) calculations, thiapillar[5]arenes are studied systematically at the ωB97XD/6-311G(d,p) level of theory. All the structures have regular pentagonal shape with the point group of D 5. The substitution of bridging methylene by sulfur leads to a significant enlargement in the molecular cavity, an extension of the spatial delocalization of the electrons, and a redshift of the absorption spectrum. The bridging groups of sulfoxide and sulfone can greatly improve the solvent effects in polar solvents, which is followed by the weakening of the pi-electron donating capacity inside the molecular cavity. Thiapillar[5]arenes have rich host–guest chemistry and can recognize a variety of guest species. Interestingly, the inclusion of thiapillar[5]arenes to ferrocene is a synergistic result of electronic and spatial effects. The sulfur-containing derivatizations of pillar[ n ]arenes are expected to expand the application prospects in supramolecular biology and electrochemistry related fields. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 03010104
- Volume :
- 581
- Database :
- Academic Search Index
- Journal :
- Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 176431942
- Full Text :
- https://doi.org/10.1016/j.chemphys.2024.112261