The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region

For non-π-conjugated [SO4] units, it is challenging to generate sufficient birefringence, owing to the high symmetry of the regular tetrahedron. Unlike the traditional trial-and-error approach, we propose a new paradigm for birefringence engineering to tune the optical properties based on [SO4] units. Through the strategy of ligand substitution, we can predict its effect on the band gap and anisotropy. Theoretical evaluations reveal generalized results that the anisotropic electron distribution of new functional groups induced by the suitable ligand substitution contributes to the band gap and birefringence. To further validate the correctness of the paradigm, we experimentally synthesized and characterized nine novel compounds with selected functional modules. By the new paradigm of ligand substitution, they can reach up to 4–6 times the birefringence of the corresponding sulfate and maintain the wide bandgap. Through rational design, (CN4H7)SO3NH2 exhibits about 35 times the birefringence of Li2SO4, which is a significant order of magnitude improvement and verifies the superiority of our proposed paradigm. This work provides a new paradigm for the modification to the non-π-conjugated group and will guide and accelerate the exploration of novel birefringent crystals in the short-wavelength region.