A Hydrogen Bonded Supramolecular Framework Birefringent Crystal

Abstract Birefringent crystals could modulate the polarization of light and are widely used as polarizers, waveplates, optical isolators, etc. To date, commercial birefringent crystals have been exclusively limited to purely inorganic compounds such as α ‐BaB 2 O 4 with birefringence of about 0.12. Herein, we report a new hydrogen bonded supramolecular framework, namely, Cd(H 2 C 6 N 7 O 3 ) 2 ⋅8 H 2 O, which exhibits exceptionally large birefringence up to about 0.60. To the best of our knowledge, the birefringence of Cd(H 2 C 6 N 7 O 3 ) 2 ⋅8 H 2 O is significantly larger than those of all commercial birefringent crystals and is the largest among hydrogen bonded supramolecular framework crystals. First‐principles calculations and structural analyses reveal that the exceptional birefringence is mainly ascribed to strong covalent interactions within (H 2 C 6 N 7 O 3 ) − organic ligands and the perfect coplanarity between them. Given the rich structural diversity and tunability, hydrogen bonded supramolecular frameworks would offer unprecedented opportunities beyond the traditional purely inorganic oxides for birefringent crystals.