P4Sn (n = 3, 5, 7): Large Birefringence Enhanced by 3D Aromaticity and Packing Effect Induced Directional π–π Noncovalent Interactions - Details

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Abstract：

Birefringent　materials　play　a　crucial　role　in　advanced　applications　such　as　nonlinear　optics,　high-density　data　storage,　and　display　technologies.　Three　birefringent　compounds,　P4S3　(1),　P4S5　(2),　and　P4S7　(3),　are　studied,　all　exhibiting　broad　transmission　in　the　range　of　≈0.38–14 µm,　with　remarkable　birefringence　values　of　0.178,　0.173,　and　0.194　@546 nm,　respectively,　surpassing　that　of　commercial　α-BaB2O4　(0.124　@546 nm).　The　relationships　between　their　topological　atomic　and　bonding　properties　and　birefringent　performance　are　established　by　high-resolution　experimental　charge　density.　The　unusual　phenomenon　of　considerable　differences　in　single　molecule　polarizability　anisotropy　among　1–3,　despite　their　similar　crystal　birefringence,　can　be　attributed　to　3D　aromaticity　and　packing　effects,　which　induce　enhanced　electron　delocalization　and　directional　noncovalent　π–π　interactions,　unprecedently　in　the　field　of　birefringent　materials.　This　work　provides　valuable　insights　for　the　design　of　new　birefringent　materials　by　leveraging　packing　effects　to　induce　favorable　charge　density　characteristics.　©　2025　Wiley-VCH　GmbH.

Keyword：

3D aromaticity birefringence charge density polarizability anisotropy

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[ 1 ] [Wu W.-L.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 2 ] [Wu W.-L.]University of Chinese Academy of Sciences, Beijing, 100049, China
[ 3 ] [Huang Y.-B.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 4 ] [Huang Y.-B.]College of Chemistry, Fuzhou University, Fujian, Fuzhou, 350116, China
[ 5 ] [Lu S.-F.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 6 ] [Lu S.-F.]University of Chinese Academy of Sciences, Beijing, 100049, China
[ 7 ] [Gao J.-S.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 8 ] [Gao J.-S.]School of Physical Science and Technology, Shanghai Tech University, Shanghai, 201210, China
[ 9 ] [Guo Y.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 10 ] [Guo Y.]University of Chinese Academy of Sciences, Beijing, 100049, China
[ 11 ] [Huang W.-Q.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 12 ] [Huang W.-Q.]University of Chinese Academy of Sciences, Beijing, 100049, China
[ 13 ] [Jing M.-N.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 14 ] [Jing M.-N.]College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China
[ 15 ] [Jiang X.-M.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 16 ] [Jiang X.-M.]University of Chinese Academy of Sciences, Beijing, 100049, China
[ 17 ] [Guo G.-C.]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou, 350002, China
[ 18 ] [Guo G.-C.]University of Chinese Academy of Sciences, Beijing, 100049, China

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Source ：

Advanced Optical Materials

ISSN： 2195-1071

Year： 2025

8 . 0 0 0

JCR@2023

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