A macrocyclic receptor containing two viologen species connected by conjugated terphenyl groups

A macrocyclic receptor molecule containing two viologen species connected by conjugated terphenyl groups has been designed and synthesised. The single-crystal X-ray structure shows that the two viologen residues have a transannular N center dot center dot center dot N separation of ca. 7.4 angstrom....

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Veröffentlicht in:Organic & biomolecular chemistry Jg. 16; H. 27; S. 5006 - 5015
Hauptverfasser: Chen, Long, Lim, Kate J. C., Babra, Tahkur S., Taylor, James O., Pizl, Martin, Evans, Robert, Chippindale, Ann M., Hartl, Frantisek, Colquhoun, Howard M., Greenland, Barnaby W.
Format: Journal Article
Sprache:Englisch
Veröffentlicht: CAMBRIDGE Royal Soc Chemistry 2018
Schlagworte:
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
STACKING
POLYMERS
NMR
CONDUCTIVITY
CONVECTION
RADICAL CATIONS
CRYSTAL-STRUCTURES
SUPRAMOLECULAR CHEMISTRY
COMPLEXATION
MOLECULES
ISSN:1477-0520, 1477-0539, 1477-0539
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Zusammenfassung:A macrocyclic receptor molecule containing two viologen species connected by conjugated terphenyl groups has been designed and synthesised. The single-crystal X-ray structure shows that the two viologen residues have a transannular N center dot center dot center dot N separation of ca. 7.4 angstrom. Thus, the internal cavity dimensions are suitable for the inclusion of pi-electron-rich species. The macrocycle is redox active, and can accept electrons from suitable donor species including triethylamine, resulting in a dramatic colour change from pale yellow to dark green as a consequence of the formation of a paramagnetic bis(radical cationic) species. Cyclic voltammetry shows that the macrocycle can undergo two sequential and reversible reduction processes (E-1/2 = -0.65 and -0.97 V vs. Fc/Fc(+)). DFT and TD-DFT studies accurately replicate the structure of the tetracationic macrocycle and the electronic absorption spectra of the three major redox states of the system. These calculations also showed that during electrochemical reduction, the unpaired electron density of the radical cations remained relatively localised within the heterocyclic rings. The ability of the macrocycle to form supramolecular complexes was confirmed by the formation of a pseudorotaxane with a guest molecule containing a p-electron-rich 1,5-dihydroxynaphthalene derivative. Threading and dethreading of the pseudorotaxane was fast on the NMR timescale, and the complex exhibited an association constant of 150 M-1 (+/- 30 M-1) as calculated from H-1 NMR titration studies.
Bibliographie:UKRI
ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1477-0520
1477-0539
1477-0539
DOI:10.1039/c8ob00919h