Electronic Communication in Confined Space Coronas of Shell-by-Shell Structured Al₂ O₃ Nanoparticle Hybrids...

A first series of examples for confined space interactions of electron-rich and electron-poor molecules organized in an internal corona of shell-by-shell (SbS)-structured Al₂ O₃ nanoparticle (NP) hybrids is reported. The assembly concept of the corresponding hierarchical architectures relies on both covalent grafting of phosphonic acids on the NPs surface (SAMs formation; SAM=self-assembled monolayer) and exohedral interdigitation of orthogonal amphiphiles as the second ligand layer driven by solvophobic interactions. The electronic communication between the chromophores of different electron demand, such as pyrenes, perylenediimides (PDIs; with and without pyridinium bromide headgroups) and fullerenes was promoted at the layer interface. In this work, it is demonstrated that the efficient construction principle of the bilayer hybrids assembled around the electronically "innocent" Al₂ O₃ core is robust enough to achieve control over electronic communication between electron-donors and -acceptors in the interlayer region. The electronic interactions between the electron-accepting and electron-donating moieties approaching each other at the layer interface were monitored by fluorescence measurements.