Importance of Precursor Adaptability in the Assembly of Molecular Organic Cages
| Autor: | Manuel Rondelli, Antonio H. Daranas, Tomás Martín |
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| Přispěvatelé: | Ministerio de Ciencia e Innovación (España), Agencia Estatal de Investigación (España), Gobierno de Canarias |
| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | The Journal of Organic Chemistry. 88:2113-2121 |
| ISSN: | 1520-6904 0022-3263 |
| Popis: | For molecular architectures based on dynamic covalent chemistry (DCvC), strict preorganization is a paradigmatic concept and the generally accepted strategy for their rational design. This results in the creation of highly rigid building blocks which are expected to fulfill the ideal geometry of the assembly, coming at a price that small geometric mismatches result in unpredicted and/or unproductive reaction outcomes. In this study, we show that feet of a tripodal platform have a great influence on the assembly of tetrahedral organic cages based on boronate ester formation. The aryl benzyl ether-functionalized building blocks perform significantly better than their alkyl-functionalized equivalents. Experimentally and using density functional theory geometry optimization of the cage structures, we prove that unexpectedly, this is not due to solubility but because of the enhanced capability of the aryl benzyl ether-functionalized building blocks to fit the ideal geometry of the assembly. This introduces the concept of building block adaptability to overcome geometrical mismatches in DCvC systems. Dedicated to Professor Fernando García Tellado on the occasion of his 65th birthday. Grants (PGC2018-094503-B-C21, PID2021-128047NB-I00, and PID2019-109476RB-C21) were funded by MCIN/AEI/10.13039/501100011033 and by “ERDF A way of making Europe” and the Canary Islands Government (ProID2020010004, ACIISI/FEDER, UE). The authors thank Dr. Jorge Pasán from the University of La Laguna for the resolution of the X-ray diffraction experiments, technician Victor Manuel de la Iglesia Rial for his experimental assistance, and Dr. Jakob Timmermann for fruitful discussions. M.R. thanks the Canary Islands Government (ACIISI) for a pre-doctoral fellowship. |
| Databáze: | OpenAIRE |
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