Fluorescence modulation in tribranched switchable [4]rotaxanes.

ABSTRACT

Two novel tribranched [4]rotaxanes with a 1,3,5-triphenylene core and three rotaxane arms have been designed, synthesized, and characterized by (1)H and (13)C NMR spectroscopies and HR-ESI mass spectrometry. [4]Rotaxanes 1 and 2 each possess the same three-armed skeleton. Each arm incorporates two distinguishable binding sites for a dibenzo[24]crown-8 ring, namely a dibenzylammonium site and an N-methyltriazolium site, and is terminated by a 4-morpholino-naphthalimide fluorophore as a stopper. [4]Rotaxane 1 has three di-ferrocene-functionalized dibenzo[24]crown-8 rings whereas 2 has three simple dibenzo[24]crown-8 rings interlocked with the thread component. Uniform shuttling motions of the three macrocycles in both 1 and 2 can be driven by external acid-base stimuli, which were confirmed by (1)H NMR spectroscopy. However, [4]rotaxanes 1 and 2 show distinct modes of fluorescence modulation in response to external acid-base stimuli. [4]Rotaxane 1 exhibits a remarkable fluorescence decrease in response to the addition of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a base, which can displace the ferrocene-functionalized macrocycle from the dibenzylammonium station to the N-methyltriazolium station. In contrast, the fluorescence intensity of [4]rotaxane 2 showed an enhancement with the addition of DBU. Time-resolved fluorescence measurements have been performed. The different photoinduced electron-transfer processes responsible for the fluorescence changes in the two molecular systems are discussed. Topological structures of this kind have significant potential for the design and construction of large and complex assemblies with controllable functions.