Water soluble molecular switches of fluorescence based on the Ni(III)/Ni(II) redox change.
The water soluble Ni(II) complexes of the cyclam derivatives with 1,3-benzodioxole and 1,2,3-trimethoxybenzene display the fluorescent emission typical of the covalently linked fluorophores, which results from a charge transfer excited state. On oxidation to Ni(III), the fluorescence is completely quenched due to the occurrence of an electron transfer (eT) process from the excited fluorogenic fragment Fl to the oxidized metal. Thus, fluorescence can be switched off/on at will, for several cycles, by consecutively oxidizing and reducing the metal center, in controlled potential electrolysis experiments both in acetonitrile and in aqueous 0.1 M HClO4. Occurrence of an eT process from Fl to Ni(III) ultimately depends upon the easy oxidation of Fl to Fl+, whereas failure of the occurrence of an eT process from Ni(II) to Fl has to be ascribed to the particular resistance of Fl fragments to the reduction.
Fabbrizzi
Luigi
L
Dipartimento di Chimica Generale, Università di Pavia, via Taramelli 12, I-27100 Pavia, Italy. fabbrizz@unipv.it
Licchelli
Maurizio
M
Mascheroni
Stefano
S
Poggi
Antonio
A
Sacchi
Donatella
D
Zema
Michele
M