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Electronic Communication in Confined Space Coronas of Shell‐by‐Shell Structured Al 2 O 3 Nanoparticle Hybrids Containing Two Layers of Functional Organic Ligands
Author(s) -
Stiegler Lisa M. S.,
Hirsch Andreas
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901052
Subject(s) - electron transfer , nanoparticle , chemistry , covalent bond , shell (structure) , monolayer , solvophobic , chemical physics , nanotechnology , molecule , materials science , photochemistry , organic chemistry , composite material
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 Al 2 O 3 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” Al 2 O 3 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.