We examined the alkali metal-recognition property and the structure of an amphiphilic crown ether azoprobes (15C5-Azo-C
n ;
n = 4, 6, 8)/cyclodextrin (CyD) complex in water by UV-Vis absorption spectroscopy and circular dichroism (CD) spectroscopy. The 15C5-Azo-C
n formed a stable complex with
γ-CyD by making
H-aggregate, and its apparent affinity was intensified by about 10 times for K
+, and not for Na
+. It was suggested that a
H-aggregate of 15C5-Azo-C4 and 15C5-Azo-C6 bound one
γ-CyD molecule, and 15C5-Azo-C8 bound one or two
γ-CyD molecules by the addition of K
+. The induced CD analysis revealed that
γ-CyD bound with both the phenylazo moiety and the alkyl chain unit of the azoprobe by the addition of K
+, although
γ-CyD bound with mainly the phenylazo moiety of azoprobe by the addition of Na
+.
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