Theoretical study on exohedral complexes C₆H₆TMB₄₀ (TM = Sc-Ni)

Area of Science:

• Computational Chemistry
• Materials Science
• Inorganic Chemistry

Background:

• Borospherene (B₄₀) is a novel fullerene-like boron cage with unique electronic properties.
• Exohedral complexes offer tunable properties by functionalizing the cage surface.
• Transition metal (TM) incorporation can significantly alter molecular stability and reactivity.

Purpose of the Study:

• To systematically investigate the structural, bonding, and electronic properties of exohedral C₆H₆TMB₄₀ complexes.
• To understand the influence of 3d transition metals on the B₄₀ cage and benzene molecule.
• To determine the ground spin states and stability of these novel complexes.

Main Methods:

• Density Functional Theory (DFT) calculations were employed for systematic investigation.
• Analysis of bonding modes (η⁷, η⁶) between transition metals and the B₄₀ cage.
• Determination of ground spin states (singlet, doublet, triplet) for various complexes.

Main Results:

• The bonding type between TM and B₄₀ transitions from η⁷ to η⁶ and back to η⁷ with increasing d electrons.
• Most C₆H₆TMB₄₀ clusters exhibit singlet ground states, with exceptions for Ti and Fe complexes (triplets).
• Ionic-covalent interactions between TM, benzene, and the B₄₀ cage contribute to enhanced stability.

Conclusions:

• The electronic structure and bonding in C₆H₆TMB₄₀ complexes are highly dependent on the TM identity.
• These complexes exhibit tunable electronic properties and enhanced stability, making them promising for future applications.
• The study provides fundamental insights into the chemistry of borospherene-based exohedral complexes.