From molecules in solution to molecules on surfaces – using supramolecular dyads to form functional self-assembled networks on graphene

Abstract

Using supramolecular chemistry to functionalise graphene for photonic applications is a challenging issue due to graphene’s capacity to quench any emission from molecules adsorbed on its surface. To overcome this...

Seeding the vertical growth of laterally coherent coordination polymers on the rutile-TiO2(110) surface

“…Even STM imaging in solution is hampered by the tip interaction with the upward dangling termination of the coordinated molecule, as formerly shown by a comparative topographic study of perylene derivatives coordinated either vertically or coplanarly to Zn-tetrapyrroles. 6 Conventional Raman infrared spectroscopy may detect the vibrational modes of a free standing molecule, 5 but lacks quantitativeness (in terms of molecular population and orientation), as well as chemical sensitivity.…”

“…Accommodation of dyads at specific sites, may be achieved by pre-patterning the surface with suitable self-assembled monolayers. 5,6 Such chemical protocols yield a poor surface homogeneity, as well as a low degree of purity. For applications in organoelectronic devices, one would rather need to control also the lateral coherence (transverse to the coordination axis direction) in order to grow recursively 2D + 1 hetero-stacked homogeneous layers.…”

Ready-to-be-addressed oxo-clusters: individualized, periodically organized and separated from the substrate

“…This task was challenging because of the technique used, the STM in air, where a huge electric field (several GV m −1 ) is applied between the tip and the sample, which can induce an alteration in the arrangement of the highly-charged POMs on the surface. 32 Nevertheless, we succeeded in several cases to image stable well-organized islands of assumed POMs in which a clear POM-to-POM separation is around 1 nm (Fig. 4).…”

“…2,12,28,29 To ensure the periodic and individualized organization of the molecules, an elegant and promising approach takes advantage of the templating effect of a bidimensional (2D) supramolecular assembly on a substrate. [30][31][32] Two previous attempts described in the literature used the pores of a porous molecular network or co-assembled POMs with self-assembling molecules, but failed to individualize the POMs (several POMs localized in molecular pores) or to thoroughly characterize the co-assembly. 33,34 In this communication, we report the first POMs properly individualized, organized and separated from the substrate.…”