OEEF-Driven Intramolecular Self-Redox of Superalkali Rb 3 BeB 6 Be'Rb' 3 : A High-Performance Candidate for NLO Molecular Switch.

To provide a novel intramolecular self-redox switch, a boron-based sandwich-like complex Rb 3 BeB 6 Be'Rb' 3 is achieved by using theoretical computations. An applicable oriented external electric field (OEEF) can result in the occurrence of intramolecular self-redox (IMSR) with a long-range electron transfer from tetrahedral Be'Rb' 3 to Rb 3 Be and subsequently [Rb 3 Be] 3+ [B 6 ] 6- [Be'Rb' 3 ] 3+ ( D 3d ) changes to [Rb 3 Be] 2+ [B 6 ] 6- [Be'Rb' 3 ] 4+ ( C 3 v ), accompanying high-performance NLO switchable effect for both static and dynamic first hyperpolarizability (β 0 ). [Rb 3 Be] 3+ [B 6 ] 6- [Be'Rb' 3 ] 3+ (off-form) owns zero of dipole moment (μ 0 ) and β 0 , while [Rb 3 Be] 2+ [B 6 ] 6- [Be'Rb' 3 ] 4+ (on-form) exhibits a μ 0 of 3.36 D and a β 0 e of 2.18 × 10 5 au. The different dynamic first hyperpolarizabilities between [Rb 3 Be] 3+ [B 6 ] 6- [Be'Rb' 3 ] 3+ and [Rb 3 Be] 2+ [B 6 ] 6- [Be'Rb' 3 ] 4+ are also significant. This indicates that Rb 3 BeB 6 Be'Rb' 3 is a potential candidate for an IMSR NLO switch.