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

[Image: see text] 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(3v)), 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.