Tb₂O@C₂(13333)-C₇₄: A Non-Isolated Pentagon Endohedral Fullerene Containing a Nearly Linear Tb-O-Tb Unit

Area of Science:

• Nanomaterials Science
• Inorganic Chemistry
• Physical Chemistry

Background:

• Fullerenes are carbon allotropes with unique cage-like structures.
• Encapsulating metal oxides within fullerenes creates novel nanomaterials with tailored properties.
• The synthesis and characterization of endohedral fullerenes are crucial for exploring their potential applications.

Purpose of the Study:

• To synthesize and characterize a novel terbium oxide cluster encapsulated within a C74 fullerene cage.
• To investigate the structural and magnetic properties of the resulting endohedral fullerene complex.
• To explore the potential of this complex as a single-molecule magnet.

Main Methods:

• Electric arc synthesis to produce azafullerene and oxide cluster endohedral fullerenes.
• Cocrystallization with Nickel(II) octaethylporphyrin (Ni(OEP)) for crystal growth.
• Single-crystal X-ray diffraction for structural determination.
• Ab initio multiconfigurational methods for magnetic property calculations.

Main Results:

• Isolation of Tb2O@C2(13333)-C74 as a byproduct of Tb2@C79N synthesis.
• Determination of a nearly linear Tb-O-Tb unit within the C74 cage.
• Unusual positioning of terbium atoms adjacent to pentalene units, deviating from the isolated pentagon rule.
• Computational prediction of strong axiality and potential as a single-molecule magnet.

Conclusions:

• Terbium oxide clusters can be successfully encapsulated within C74 fullerene cages.
• The unique structure of Tb2O@C2(13333)-C74 influences its electronic and magnetic properties.
• This endohedral fullerene complex shows promise as a single-molecule magnet due to predicted large magnetic anisotropy.