Investigation of an acid-base and redox molecular switch: From bulk the single-molecule level

被引:32
作者
Al-Kaysi, Rabih O.
Luis Bourdelande, Jose
Gallardo, Iluminada
Guirado, Gonzalo [1 ]
Hernando, Jordi
机构
[1] Univ Autonoma Barcelona, Dept Quim, Cerdanyola Del Valles 08193, Spain
[2] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA
关键词
electron transfer; Meisenheimer complex; molecular switch; single-molecule studies; zwitterionic complex;
D O I
10.1002/chem.200700236
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this work we investigate a new fluorescent molecular switch based on the interconversion between the fluorescent zwitterionic form (ZW1)and the non-fluorescent anionic state (MC2) of a spirocyclic Meisenheimer complex of 1,3,5-trinitrobenzene. Density functional theory molecular orbital calculations reveal that photo-induced electron transfer from a guanidine group to the trinitrocyclohexadiene fluorophore of the complex quenches the emission from MC2. Protonation, as well as coordination of other Lewis acids to the guanidine group, suppress the quenching mechanism and allow the complex to fluoresce. In agreement with the calculations, reversible on-off fluorescence switching of the ZW1-MC2 bulk system occurs by protonation-deprotonation of the guanidine moiety upon acid-base addition. Interestingly, spectroelectrochemical ensemble measurements show that switching of the ZW1-MC2 pair can also be attained electrochemically, thus unraveling the versatile functioning of this system. The ultimate limit of monitoring the reversible on-off operation of individual switch molecules is reached by means of single-molecule fluorescence spectroscopy, which demonstrates the potential of the ZW1-MC2 system to be used as a true single-molecule switch on the nanometer scale.
引用
收藏
页码:7066 / 7074
页数:9
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