Spacer-chromoionophores — polymethine dye substituted aza-crown ethers with increased complexation ability

Aromatic aldehyde derivatives of N-phenyl-aza-15-crown-5 ( 2 ), N-phenyl-aza-18-crown-6 ( 8 ), and benzo-15-crown-5 ( 10 ) are condensed with malononitrile and 2-amino-1,1,3-tricyano-1-propene to give light yellow to orange colored crown ether derivatives 4 , 5a , 9a , 11 , and 12 . 5a and 9a were acylated with ethyl chloroformate to give the magenta colored dyes 5b and 9b , respectively. By condensation of N-(4-nitrosophenyl)-aza-15-crown-5 3 with 2-amino-1,1,3-tricyano-1-propene the magenta dye 6a is obtained. Acylation of 6a with ethyl chloroformate leads to the deep blue colored dye 6b . In these derivatives the nitrogen or oxygen atoms of the crown ethers are part of the chromophoric system, and binding properties are affected. Further chromophoric derivatives of aza-crown ethers are studied in which these are separated from the chromophoric moiety by a spacer. N-(ω-chloroalkyl)-N-alkylanilines 14a-c were attached to aza-15-crown-5 13a-c and aza-18-crown-6 13b-c to yield the spacer crown ether derivatives 15a-c and 16a-c , respectively. The formylated spacer crown ether derivatives 17a-c and 18b were condensed with 2-amino-1,1,3-tricyano-1-propene to give the orange spacer-chromoionophores 19a-c and 20 . In these crown ether derivatives the extended conjugation is interrupted by the spacer, and good binding properties are obtained. The complex formation constants of the crown ether derivatives with Na⁺ and K⁺ are determined using ¹H NMR spectroscopy.