A Covalent Organic Helical Cage with Remarkable Chiroptical Amplification

Purely organic shape‐persistent chiral cages are designed through the use of rigid chiral axes. Covalent dimerization of a tripodal fragment bearing chiral allenes forms a molecular twisted prism with loop‐like lateral edges presenting 10‐fold chiroptical amplification compared to its isolated build...

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Bibliographic Details
Published in:Chemistry : a European journal 2015-12, Vol.21 (50), p.18085-18088
Main Authors: Míguez-Lago, Sandra, Llamas-Saiz, Antonio L., Magdalena Cid, M., Alonso-Gómez, J. Lorenzo
Format: Article
Language:English
Subjects:
Amplification
Cage
Chemistry
chirality
circular dichroism
Containers
Covalence
Crystal structure
Dichroism
Dimerization
Helical
helicity
host-guest
molecular cages
Rods
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Summary:Purely organic shape‐persistent chiral cages are designed through the use of rigid chiral axes. Covalent dimerization of a tripodal fragment bearing chiral allenes forms a molecular twisted prism with loop‐like lateral edges presenting 10‐fold chiroptical amplification compared to its isolated building blocks. The expected geometry of covalent organic helical cage (M,M)3‐1 was confirmed by X‐ray crystal structure analysis. Comparison of the chiroptical responses of this shape‐persistent molecular container with more flexible analogues highlights how the control of the conformational freedom of the molecule can be used to obtain molecular cages with strong chiroptical responses. Selective inclusion‐complex formation with ferrocenium ions [(P,P)3‐1@Fc+] was confirmed and quantified with HR‐ESI‐MS and NMR spectroscopy. Make it helical: The combination of chiral axes (spheres/rods) with aromatic bases (triangle) was used to construct a covalent organic helical cage with remarkable chiroptical amplification. This shape‐persistent molecular container selectively forms an inclusion complex with ferrocenium ions. ECD=electronic circular dichroism.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201503994