Chiral Dibenzopentalene-Based Conjugated Nanohoops through Stereoselective Synthesis.
antiaromaticity
chiral macrocycles
chiral resolution
cycloparaphenylenes
fullerenes
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
03 May 2021
03 May 2021
Historique:
revised:
16
02
2021
received:
21
12
2020
pubmed:
18
2
2021
medline:
18
2
2021
entrez:
17
2
2021
Statut:
ppublish
Résumé
Conjugated nanohoops allow to investigate the effect of radial conjugation and bending on the involved π-systems. They can possess unexpected optoelectronic properties and their radially oriented π-system makes them attractive for host-guest chemistry. Bending the π-subsystems can lead to chiral hoops. Herein, we report the stereoselective synthesis of two enantiomers of chiral conjugated nanohoops by incorporating dibenzo[a,e]pentalenes (DBPs), which are generated in the last synthetic step from enantiomerically pure diketone precursors. Owing to its bent shape, this diketone unit was used as the only bent precursor and novel "corner unit" in the synthesis of the hoops. The [6]DBP[4]Ph-hoops contain six antiaromatic DBP units and four bridging phenylene groups. The small HOMO-LUMO gap and ambipolar electrochemical character of the DBP units is reflected in the optoelectronic properties of the hoop. Electronic circular dichroism spectra and MD simulations showed that the chiral hoop did not racemize even when heated to 110 °C. Due to its large diameter, it was able to accommodate two C60 molecules, as binding studies indicate.
Identifiants
pubmed: 33596338
doi: 10.1002/anie.202016968
pmc: PMC8252646
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
10680-10689Subventions
Organisme : Deutsche Forschungsgemeinschaft
ID : 230408635
Organisme : Deutsche Forschungsgemeinschaft
ID : 434040413
Organisme : Deutsche Forschungsgemeinschaft
ID : INST 40/467-1 FUGG
Organisme : Deutsche Forschungsgemeinschaft
ID : INST 39/1081-1 FUGG
Informations de copyright
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
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