Halogen Bond Unlocks Ultra‐High Birefringence

Abstract

AbstractAnisotropy is crucial for birefringence (Δn) in optical materials, but optimizing it remains a formidable challenge (Δn >0.3). Supramolecular frameworks incorporating π‐conjugated components are promising for achieving enhanced birefringence because of their structural diversity and inherent anisotropy. Herein, we first synthesized (C6H6NO2)+Cl− (NAC) and then constructed a halogen‐bonded supramolecular framework I+(C6H4NO2)− (INA) by halogen aliovalent substitution of Cl− with I+. The organic moieties are protonated and deprotonated nicotinic acid (NA), respectively. The antiparallel arrangement of birefringent‐active units in NAC and INA leads to significant differences in the bonding characteristics between the interlayer and intralayer domains. Moreover, the [O⋅⋅⋅I+⋅⋅⋅N] halogen bond in 1D [I+(C6H4NO2)−] chain exhibits stronger interactions and stricter directionality, resulting in a more pronounced in‐plane anisotropy between the intrachain and interchain directions. Consequently, INA exhibits exceptional birefringent performance, with a value of 0.778 at 550 nm, twice that of NAC (0.363 at 550 nm). This value significantly exceeds those of commercial birefringent crystals, such as CaCO3 (0.172 at 546 nm), and is the highest reported value among ultraviolet birefringent crystals. This work presents a novel design strategy that employs halogen bonds as connection sites and modes for birefringent‐active units, opening new avenues for developing high‐performance birefringent crystals.