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<p>Linking two Li(HCN)<sub>3</sub> by alkali earth metal atom, L–L and S–S configurations of formed double-headed Li[(HCN)<sub>3</sub>&#xa0;M(HCN)<sub>3</sub>]Li (M = Ca, Sr and Ba), respectively, have two large and two small heads, while both S–L and L–S own one large and one small head. The DFT results show L–L, S–L and L–S configurations feature well-performance mixed-valence superalkalide behaviour that L–L has an alkalide-alkaline earth-alkalide interaction of Li<sup>−</sup>[(HCN)<sub>3</sub>M<sup>2+</sup>(HCN)<sub>3</sub>]Li<sup>−</sup> and belongs to Robin–Day class III mixed-valence compound (MVC) with two identical redox centres, while S–L and L–S, respectively, possess leftward (Li<sup>−</sup>[(HCN)<sub>3</sub><sup>−</sup>M<sup>2+</sup>(HCN)<sub>3</sub><sup>−</sup>]Li<sup>+</sup>) and rightward alkali-alkaline earth-alkalide interactions (Li<sup>+</sup>[(HCN)<sub>3</sub><sup>−</sup>M<sup>2+</sup>(HCN)<sub>3</sub><sup>−</sup>]Li<sup>−</sup>) and are part of class II MVCs due to the uneven-redox-centres. The different redox centres in Li[M(HCN)<sub>6</sub>]Li bring significantly different IR vibration modes or different intensities and frequencies of the same vibration. From symmetric L–L and S–S to unsymmetric L–S and L–S, the double-pole double-throw (DPDT) nonlinear optical (NLO) molecular switchable effect is exhibited.</p> Graphical Abstract <p></p>

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Theoretical study on the double-headed Li[(HCN)3M(HCN)3]Li (M = Ca, Sr and Ba) as new kind of Robin-Day-type mixed-valence superalkalides: structures, IR spectra, and NLO switching effects

  • 期刊论文

  • 发表日期：

    2026年5月6日

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  • Jin-Jin Wei,
  • Zhong-Hao Du,
  • Hao Chen,
  • Fan Zhong,
  • Yin Lin,
  • Jin-Hua Cai,
  • Zhi-Jun Wang,
  • Hongliang Xu,
  • Yin-Feng Wang

摘要

Linking two Li(HCN)3 by alkali earth metal atom, L–L and S–S configurations of formed double-headed Li[(HCN)3 M(HCN)3]Li (M = Ca, Sr and Ba), respectively, have two large and two small heads, while both S–L and L–S own one large and one small head. The DFT results show L–L, S–L and L–S configurations feature well-performance mixed-valence superalkalide behaviour that L–L has an alkalide-alkaline earth-alkalide interaction of Li−[(HCN)3M2+(HCN)3]Li− and belongs to Robin–Day class III mixed-valence compound (MVC) with two identical redox centres, while S–L and L–S, respectively, possess leftward (Li−[(HCN)3−M2+(HCN)3−]Li+) and rightward alkali-alkaline earth-alkalide interactions (Li+[(HCN)3−M2+(HCN)3−]Li−) and are part of class II MVCs due to the uneven-redox-centres. The different redox centres in Li[M(HCN)6]Li bring significantly different IR vibration modes or different intensities and frequencies of the same vibration. From symmetric L–L and S–S to unsymmetric L–S and L–S, the double-pole double-throw (DPDT) nonlinear optical (NLO) molecular switchable effect is exhibited.

Graphical Abstract