Citation: Miao-Bin Xu, Qian-Qian Chen, Bing-Xuan Li, Ke-Zhao Du, Jin Chen. π-Lone pair synergy in (C₇H₄NO₄)(IO₃): Optimal balance among SHG, birefringence, and bandgap performance[J]. Chinese Chemical Letters, ;2025, 36(11): 110513. doi: 10.1016/j.cclet.2024.110513 shu

π-Lone pair synergy in (C₇H₄NO₄)(IO₃): Optimal balance among SHG, birefringence, and bandgap performance

Miao-Bin Xu ^a ,
Qian-Qian Chen ^b ,
Bing-Xuan Li ^b ,
Ke-Zhao Du ^a ,
Jin Chen ^{a, b, *,}

a.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350002, China
b.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

cj2015@fjne.edu.cn

Received Date: 6 August 2024
Revised Date: 4 September 2024
Accepted Date: 26 September 2024
Available Online: 28 September 2024

Figures(3)

Birefringence and second harmonic generation (SHG) are important optical properties of functional crystals. However, it is relatively rare for a compound to exhibit both enhanced properties simultaneously. In this study, we used DFT calculations to discover an ideal functional gene: protonated 3, 5-dipicolinic acid (C₇H₄NO₄, HDPA). By combining HPDA with the traditional IO₃^- anion, we obtained a non-centrosymmetric and polar semiorganic iodate, namely HDPA(IO₃). The organic cations and iodate anions in HDPA(IO₃) are bridged via the N-H···O and O-H···O hydrogen bonds, forming the wave-shaped layers. The synergistic effect between the expanded π-conjugation of the organic cation and the stereochemically active lone pair electrons in the inorganic iodate anion results that HDPA(IO₃) exhibiting a strong SHG effect, 3.6 times that of KH₂PO₄, and an unusually large birefringence of 0.35 at 546 nm, larger than most of SHG-active iodates. Additionally, HDPA(IO₃) has a wide bandgap of 4.12 eV with a corresponding cutoff edge at 269 nm, indicating its potential as a promising short-wave ultraviolet (UV) optical crystal.
- Iodate-based crystal,
- Large SHG response,
- Wide bandgap,
- Giant birefringence,
- Optimized balance,
- π-Lone pair synergetic
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π-Lone pair synergy in (C₇H₄NO₄)(IO₃): Optimal balance among SHG, birefringence, and bandgap performance