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. 2025 Aug 4;64(32):e202508997.
doi: 10.1002/anie.202508997. Epub 2025 Jun 5.

Giant Birefringence and Solar-Blind Ultraviolet Transmission by Coordination-Induced Assembly of π-Conjugated Pyridine-Carboxylate

Peng-Hui Guo  1 , Xia Zhang  1 , Yao Guo  2 , Nan Zhang  1 , Yi-Gang Chen  1 , Xingxing Jiang  3 , Zheshuai Lin  3 , Xian-Ming Zhang  1   4
Affiliations

Giant Birefringence and Solar-Blind Ultraviolet Transmission by Coordination-Induced Assembly of π-Conjugated Pyridine-Carboxylate

Peng-Hui Guo et al. Angew Chem Int Ed Engl. .

Abstract

Giant birefringent crystal with large bandgap is of paramount importance for modern optical devices but simultaneous achievement of giant birefringence and large bandgap is a great challenge stemming from their inherent contradictory relationship according to Kramers‒Kronig equation. Herein, an organic-inorganic hybrid uniformly-stacked 2D crystal [Be2(μ-OH)2(C7H3NO4)(H2O)]·H2O (I) was successfully synthesized by a molecular crystal engineering involving hydrogen bond synthons. Layered I features new [Be2O2N(μ-OH)2(H2O)]∞ helical chain composed of BeII tetrahedral coordination, and the strong covalent BeII cations coordinate with the O and N atoms on birefringence-active π-conjugated (C7H3NO4)2- organic groups with optimal spatial arrangement. As a result, I demonstrates the largest birefringence of 0.6 in the solar-blind UV spectral region, with large bandgap of 4.75 eV and short UV absorption edge of 261 nm. First-principles calculations and structural analyses uncover that the superior optical properties mainly originate from collective effects of highly-active (C7H3NO4)2- groups, distorted Be-tetrahedral units, and their uniform stacking. This work not only provides a potential solar-blind UV birefringent crystal for rapidly increasing number of optical applications but also a new chance for the rational design of wide UV giant birefringent crystals.

Keywords: Bandgap; Birefringence; Hydrogen bond; Ultraviolet; π‐Conjugated.

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