Synthesis of Dansyl-Substituted Cryptands Containing Triaza­cycloalkane Moieties and their Evaluation as Fluorescent Chemosensors

Dedicated to Professor Victor Snieckus

Abstract

A method for the synthesis of a new family of cryptands containing 1,4,7-triazacyclononane and 1,5,9-triazacyclododecane moieties and dansyl fluorophore groups has been elaborated starting from free triazacycloalkanes and employing Pd(0)-catalyzed amination at the macrocyclization step. The dependence of the products yields on the nature of reagents has been established. The majority of synthesized macrobicycles have been evaluated as possible chemosensors for detecting metal cations. Compound comprising 1,4,7-triazacyclononane and dioxadiamine linker proved to be a prospective colorimetric sensor for Cu(II) by changing its absorption spectrum in the presence of this cation, while other cryptands demonstrated full quenching of fluorescence in the presence of Cu(II) and Al(III) what makes them promising fluorescent molecular probes for these metals.

Key words

triazacycloalkanes - cryptands - Pd catalysis - amination - ­fluorescence - cations detection

• References and Notes

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• 26 The experiments of metal cations detection were conducted as follows. The solutions of Zn(II), Cd(II), Pb(II), Hg(II), Ag(I), Cu(II), Co(II), Ni(II), Fe(II), Mn(II), Mg(II), Ba(II), Ca(II), Al(III), Li(I) Na(I), K(I) perchlorates and In(III), Y(III), Ga(III) nitrates were dissolved in MeCN (UHPLC grade) to make concentrations c = 0.01 M [in the case of Hg(II) perchlorate 0.005 M]. Macrocyclic ligands 14–17 were also dissolved in MeCN (UHPLC grade) to make concentrations c = 3.3 × 10^–5 M. The solution of metal salt was added directly to the solution of the ligand in the spectrophotometric cuvette (1, 2, 5 equiv) and UV–vis and fluorescent spectra (excitation at 340 nm) were recorded after each addition.
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