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Peer-reviewedCC BYScience Advances

Breaking the tetrahedral constraint of tetracoordination: Square-planar [ICl ₄ ] enables unprecedented birefringence in [C(NH ₂ ) ₃ ][ICl ₄ ]

  • Zhiwei Sun1
  • Qingran Ding1
  • Weiqi Huang2
  • Peixuan Zhu1
  • Guimei Lai1
  • Xue Mei1
  • Sangen Zhao3
  • Junhua Luo1,2
  1. 1College of Chemistry and Materials, Jiangxi Normal University, Nanchang, Jiangxi, 330022, P. R. China.
  2. 2State Key Laboratory of Functional Crystals and Devices, Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter, Fuzhou, Fujian, 350002, P. R. China.
  3. 3Quantum Science Center of Guangdong-Hong Kong-Macao Greater Bay Area, Shenzhen, Guangdong, 518000, P. R. China.
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Abstract

Birefringent crystals are indispensable for optoelectronic applications, yet commercially available crystals still suffer from the drawback of insufficient birefringence. Meanwhile, tetracoordination units—traditionally confined to a tetrahedral geometry—have long been sidelined from mainstream high-performance birefringent materials due to their intrinsic nearly negligible polarizability anisotropy. Herein, we break this tetrahedral constraint—demonstrating tetracoordinate square-planar [ICl 4 ] anions as a revolutionary platform for unprecedented birefringence. To achieve this, we report an improved synthesis method that avoids the use of toxic Cl 2 gas, enabling the preparation of [C(NH 2 ) 3 ][ICl 4 ] featuring square-planar [ICl 4 ] units. This compound displays a birefringence of 0.975@550 nm, setting a new record that surpasses all existing compounds containing tetracoordinate structural units. The giant birefringence of this material is attributed to the strong polarization anisotropy induced by the unique square-planar geometry of the [ICl 4 ] tetracoordinate units. This research provides theoretical guidance for designing high-performance polar materials based on tetracoordinate units in giant birefringent materials and promotes applications in related optoelectronic device.

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Cite

BibTeXRIS
BibTeX
@article{sun2026breaking,
  title = {{Breaking the tetrahedral constraint of tetracoordination: Square-planar [ICl ₄ ] enables unprecedented birefringence in [C(NH ₂ ) ₃ ][ICl ₄ ]}},
  author = {Zhiwei Sun and Qingran Ding and Weiqi Huang and Peixuan Zhu and Guimei Lai and Xue Mei and Sangen Zhao and Junhua Luo},
  journal = {Science Advances},
  year = {2026},
  month = oct,
  doi = {10.1126/sciadv.aef7948},
  url = {https://www.science.org/doi/10.1126/sciadv.aef7948},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Breaking the tetrahedral constraint of tetracoordination: Square-planar [ICl ₄ ] enables unprecedented birefringence in [C(NH ₂ ) ₃ ][ICl ₄ ]
AU  - Zhiwei Sun
AU  - Qingran Ding
AU  - Weiqi Huang
AU  - Peixuan Zhu
AU  - Guimei Lai
AU  - Xue Mei
AU  - Sangen Zhao
AU  - Junhua Luo
PY  - 2026
DA  - 2026/10/16
JO  - Science Advances
DO  - 10.1126/sciadv.aef7948
UR  - https://www.science.org/doi/10.1126/sciadv.aef7948
AB  - Birefringent crystals are indispensable for optoelectronic applications, yet commercially available crystals still suffer from the drawback of insufficient birefringence. Meanwhile, tetracoordination units—traditionally confined to a tetrahedral geometry—have long been sidelined from mainstream high-performance birefringent materials due to their intrinsic nearly negligible polarizability anisotropy. Herein, we break this tetrahedral constraint—demonstrating tetracoordinate square-planar [ICl 4 ] anions as a revolutionary platform for unprecedented birefringence. To achieve this, we report an improved synthesis method that avoids the use of toxic Cl 2 gas, enabling the preparation of [C(NH 2 ) 3 ][ICl 4 ] featuring square-planar [ICl 4 ] units. This compound displays a birefringence of 0.975@550 nm, setting a new record that surpasses all existing compounds containing tetracoordinate structural units. The giant birefringence of this material is attributed to the strong polarization anisotropy induced by the unique square-planar geometry of the [ICl 4 ] tetracoordinate units. This research provides theoretical guidance for designing high-performance polar materials based on tetracoordinate units in giant birefringent materials and promotes applications in related optoelectronic device.
SN  - 2375-2548
ER  -