Novel inorganic aromatic mixed-valent superalkali electride CaN3Ca: an alkaline-earth-based high-sensitivity multi-state nonlinear optical molecular switch

Focusing on innovative high-performance single-pole double-throw nonlinear optical (NLO) molecular switches, two C3v configurations (1 and 3) and one D3h configuration (2) of bipyramidal CaN3Ca have been obtained by using quantum mechanical methods. Not only are 1, 2, and 3 alkaline-earth-based aromatic superalkalis, but they are also interesting electrides. The salt-like electronic structures of e−⋯Ca2+N33−Ca2+ (1) and Ca2+N33−Ca2+⋯e− (3) with localized redox centres are rare inorganic Robin–Day class II-type structures, and e0.5−⋯Ca2+N33−Ca2+⋯e0.5− (2) with a delocalized structure is a class III-type mixed-valent superalkali electride. Under a small external electric field of ±0.0110 a.u. (0.565 V Å−1), the short-distance hopping of Ca atoms in CaN3Ca from the D3h configuration with in-plane aromaticity to each C3v configuration with out-of-plane aromaticity brings about the long-range transfer of half an electron from one Ca atom to another. And, subsequently, a large dipole moment (μ0) and remarkable static first hyperpolarizability (β0) occur. μz and βzzz range from 0 (D3h, off form) to −12.1 or 12.1 D (C3v, on forms) and from 0 (D3h, off form) to −19 428 or 19 428 a.u. (C3v, on forms), respectively. These extremely large differences in μz and βzzz values between the D3h and each of the C3v configurations confirm the potential of these inorganic aromatic Robin–Day-type superalkali electrides for applications in high-sensitivity multi-state nonlinear optical switches.