Nonlinear Optical Switching Driven by the Lone Pair Electron Effect in a Hybrid Compound: (1S, 4S)‐(+)‐2‐Aza‐5‐oxabicyclo[2.2.1] heptane)2[SbCl5]

• Published in: European journal of inorganic chemistry 2023-03, Vol.26 (8), p.n/a
• Main Authors: An, Zhen, Liao, Rong‐Meng, Yao, Hai‐Quan, Cheng, Yan, Zhu, Bing‐Jun, Li, Jian‐Rong, Ye, Heng‐Yun
• Format: Article
• Language: English
• Subjects: Chemical synthesis; Coordination; Coordination distortion; Distortion; Electrons; Functional coordination compounds; Heptanes; Inorganic chemistry; Lone pair electrons; Molecular dynamics; Noise levels; Nonlinear optics; Optical switching; Organic compounds; Phase transitions; Photoelectric effect; Photoelectricity; Second harmonic generation
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.202200740

In order to take advantage of hybrid materials in their structural diversity and richness of their photoelectric properties, the research in polar materials has been extended to metal‐organic compounds in recent years. The main synthesis strategy is to use the molecular dynamics. Here, we describe that the second harmonic generation (SHG) switching effect can be effectively achieved by combination of coordination distortion of metal ions with s2 electrons and molecular dynamics. We synthesized a noncentrosymmetric complex, (1S,4S)‐(+)‐2‐aza‐5‐oxabicyclo[2.2.1]heptane)2[SbCl5], and found that it undergoes an isomorphic phase transition at 382 K. Accompanying the phase transition, the SHG experiences a switching process, and its strength changes from 0.2 times of that of KDP to only noise level. Systematic characterization reveals that the significant change of coordination distortion of the Sb3+ and the change of thermal motion of organic cations lead to the SHG switching effect. This finding shows that the combination of lone pair electron effect of metal ion and molecular dynamics characteristics would be a feasible strategy in development of polar hybrid materials. A chiral organic‐inorganic hybrid compound (1S, 4S)‐(+)‐2‐Aza‐5‐oxabicyclo[2.2.1]heptane)2[SbCl5] was constructed and found to show SHG switching effect at transition temperature 382 K. The SHG switching effect is due to the coordination distortion caused by the lone pair electron effect. This finding reveals that the lone pair electron effect might be an effective element in the synthesis of polar hybrid materials.