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Endohedral Hydrogen Bonding Templates the Formation of a Highly Strained Covalent Organic Cage Compound
Please always quote using this URN: urn:nbn:de:bvb:20-opus-256762
- A highly strained covalent organic cage compound was synthesized from hexahydroxy tribenzotriquinacene (TBTQ) and a meta-terphenyl-based diboronic acid with an additional benzoic acid substituent in 2’-position. Usually, a 120° bite angle in the unsubstituted ditopic linker favors the formation of a [4+6] cage assembly. Here, the introduction of the benzoic acid group is shown to lead to a perfectly preorganized circular hydrogen-bonding array in the cavity of a trigonal-bipyramidal [2+3] cage, which energetically overcompensates the additionalA highly strained covalent organic cage compound was synthesized from hexahydroxy tribenzotriquinacene (TBTQ) and a meta-terphenyl-based diboronic acid with an additional benzoic acid substituent in 2’-position. Usually, a 120° bite angle in the unsubstituted ditopic linker favors the formation of a [4+6] cage assembly. Here, the introduction of the benzoic acid group is shown to lead to a perfectly preorganized circular hydrogen-bonding array in the cavity of a trigonal-bipyramidal [2+3] cage, which energetically overcompensates the additional strain energy caused by the larger mismatch in bite angles for the smaller assembly. The strained cage compound was analyzed by mass spectrometry and \(^{1}\)H, \(^{13}\)C and DOSY NMR spectroscopy. DFT calculations revealed the energetic contribution of the hydrogen-bonding template to the cage stability. Furthermore, molecular dynamics simulations on early intermediates indicate an additional kinetic effect, as hydrogen bonding also preorganizes and rigidifies small oligomers to facilitate the exclusive formation of smaller and more strained macrocycles and cages.…
Author: | Natalie Schäfer, Michael Bühler, Lisa Heyer, Merle I. S. Röhr, Florian BeuerleORCiD |
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URN: | urn:nbn:de:bvb:20-opus-256762 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Organische Chemie |
Language: | English |
Parent Title (English): | Chemistry—A European Journal |
Year of Completion: | 2021 |
Volume: | 27 |
Issue: | 19 |
Pagenumber: | 6077–6085 |
Source: | Chemistry—A European Journal 2021, 27(19):6077–6085. DOI: 10.1002/chem.202005276 |
DOI: | https://doi.org/10.1002/chem.202005276 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 547 Organische Chemie |
Tag: | boronate esters; cage compounds; density functional calculations; dynamic covalent chemistry; hydrogen bonding |
Release Date: | 2022/03/07 |
Licence (German): | CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International |