DFT and DFT-D studies on molecular structure of double-decker phthalocyaninato-terbium(III) complex

Abstract

A molecular structure of a double-decker phthalocyaninato-terbium(III) anion (TbPc₂⁻) is optimised by density functional theory (DFT) and DFT with a dispersion interaction (DFT-D) method. The DFT-D method such as B3LYP-D and B97-D functional sets estimates phthalocyaninato (Pc) ions to be planar although B3LYP and PBE1PBE make them concave. In addition, the planar structure corresponds to an experimental X-ray crystallographic result. On the other hand, an optimised geometry of Pc²⁻ dimer by B3LYP-D estimates the convex Pc²⁻ structure due to the dispersion interaction between outer aromatic rings. These results suggest the importance of the dispersion interaction for the structure of TbPc₂⁻.

Keywords:

• double-decker phthalocyaninato-terbium(III) anion
• TbPc₂⁻
• dispersion interaction
• DFT-D

Acknowledgements

The authors thank Professor Yamashita and Dr. Katoh for giving us many suggestions about the experimental results. This work has been supported by JST, CREST.