Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C₁₈ to C₁₆.

Area of Science:

• * Supramolecular chemistry and materials science.
• * Computational chemistry and theoretical physics.

Background:

• * Recent synthetic advancements enable the creation of novel cyclocarbon molecules.
• * On-surface chemistry and tip-induced reactions are key formation methods.
• * Cyclocarbons are being explored for their unique electronic properties.

Purpose of the Study:

• * To computationally investigate the electronic properties of C16 and C18 cyclocarbons.
• * To analyze van der Waals (vdW) complexes of cyclocarbons with donor and acceptor molecules.
• * To understand the dynamics of photoinduced electron transfer (ET) in these systems.

Main Methods:

• * Density Functional Theory (DFT) calculations.
• * Analysis of van der Waals interactions and complex formation.
• * Calculation of reorganization energies and electron transfer rates.

Main Results:

• * Cyclocarbon molecules exhibit significant electron-withdrawing capabilities.
• * vdW complexes show thermodynamically favorable photoinduced electron transfer from donors to cyclocarbons.
• * Electron transfer occurs on a picosecond timescale.
• * C16 demonstrates faster ET reactions than C18 due to lower reorganization energy.

Conclusions:

• * Cyclocarbons are promising candidates for electron acceptor materials.
• * The electron transfer dynamics are highly dependent on molecular structure and properties.
• * C16 and C18 show potential for applications in molecular electronics and photocatalysis.