Enhancement of the second hyperpolarizability by dσ electrons in one-dimensional tetrametallic transition-metal systems

The second hyperpolarizabilities (γ) of the one-dimensional Cr(II) and Mo(II) tetrametallic systems are investigated by focusing on their dependences on the open-shell singlet characters and by comparing with those of their dimetallic analogs. Significant enhancements of γ are observed in tetrametallic systems, which are attributed to the dσ electrons with an intermediate open-shell character. The present results enable us to extend the concept of 'σ-dominant third-order NLO' obtained in dimetallic transition-metal systems to general one-dimensional polymetallic systems.

93Highlights► Second hyperpolarizabilities (γ) of linearly-aligned Cr(II)4 and Mo(II)4. ► The dσ electrons with an intermediate open-shell character significantly enhance. ► A novel class of σ-dominant NLO systems.