Supramolecular Frameworks from Graphene Edge-Grafted with Ni-Salphen Complexes and Pd-PTA Linkers

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Nanotechnology

Background:

• Edge oxidized graphene oxide (EOGO) is an underexplored 2D material for supramolecular applications.
• Noncovalent reticulation offers a pathway for constructing complex molecular architectures.

Purpose of the Study:

• To construct graphene supramolecular frameworks (GSFs) using EOGO and a palladium ditopic guest linker (Pd-PTA).
• To investigate the host-guest interactions and assembly behavior of these novel supramolecular systems.

Main Methods:

• Synthesis of supramolecular complexes involving EOGO, Ni-Salphen scaffolds, and Pd-PTA.
• Spectrophotometric titrations and solid-state evaluations to characterize stoichiometry and assembly.
• Analysis of cooperative oligomerization using Hill plots and fluorescence spectroscopy.

Main Results:

• EOGO-based hybrid frameworks exhibit a stoichiometric inversion compared to simpler systems, favoring 1:1 [Ni]/[Pd-PTA] interactions.
• Successful formation of host-guest-host interconnections and cooperative oligomerization was observed.
• Kinetically controlled assembly and solvent evaporation led to long-range ordered arrangements in the solid state.

Conclusions:

• The developed method enables the construction of next-generation supramolecular frameworks with tunable properties.
• EOGO serves as a versatile building block for creating complex, ordered supramolecular architectures.
• This work highlights the potential of noncovalent interactions in designing advanced graphene-based materials.