Synthesis and immobilization of molecular switches onto titaniumdioxide nanowires

The precursor [FeIII(L)Cl (L = N,N′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN)8]4− yields a star shaped nona-nuclear cluster, [MoIV{(CN)FeIII(L)}8]Cl4. This Fe8Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mössbauer spectroscopy. This molecule was deposited on TiO2 nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis spectroscopy (high-resolution) transmission electron microscopy ((HR)TEM) and Mössbauer spectroscopy. High- and low-temperature Mössbauer spectra indicate that the spin state transition of the free cluster molecules is preserved after surface binding. The above results emphasize the possibility of fabricating molecule-based low-dimensional structures by using traditional bottom-up approaches based on the electrostatic interaction between the cluster cations and polymer functionalized nanowires. These results can be generalized for the application to both charged and non-charged molecules.

Graphical abstractApplication of molecular switches as functional units requires the addressing individual molecules, which is imaging, probling, and eventually manipulating individual molecules. In this contribution we describe the immobilization of switchable [(LFeIIINC)8MoIV]4+ units onto the surface of TiO2 nanowires using electrostatic interactions.Figure optionsDownload full-size imageDownload as PowerPoint slide