Intercage electron transfer driven by electric field in Robin-Day-type molecules.

Area of Science:

• Physical Chemistry
• Materials Science
• Quantum Chemistry

Background:

• Double-cage molecular anions offer unique platforms for studying electron behavior.
• Fluorinated fullerene derivatives present interesting electronic properties.
• Mixed-valence compounds are crucial for understanding electron delocalization and transfer.

Purpose of the Study:

• To report a new class of intercage electron-transfer isomers for fluorinated double-cage molecular anions.
• To investigate the electronic structure and redox properties of these novel isomers.
• To explore pathways for intercage electron transfer within these systems.

Main Methods:

• Computational chemistry methods were employed to model the molecular anions.
• Density Functional Theory (DFT) calculations were used to determine electronic configurations and energies.
• Analysis of electron distribution and redox states within the C(20)F(18) cages.

Main Results:

• Three intercage electron-transfer isomers (1, 2, and 3) of e(-)@C(20)F(18)(NH)(2)C(20)F(18) were identified.
• The C(20)F(18) cages exhibit nonmetal mixed-valence states (0 and -1).
• Two distinct pathways for intercage electron transfer were elucidated, influenced by electric fields and electronic excitations.

Conclusions:

• The identified isomers represent a new class of nonmetal mixed-valent compounds, potentially analogous to Robin-Day Class II and III.
• Intercage electron transfer can be controlled via external electric fields and photoexcitation.
• Isomer 2 may act as a transition state in the electron transfer process from isomer 1 to 3.