Pb₂Ba₃(BO₃)₃Cl: A Material with Large SHG Enhancement Activated by Pb-Chelated BO₃ Groups

Pb­(II) has long been associated with lone pair activity and is often substituted in alkali earth metal borates to create new nonlinear optical (NLO) materials with enhanced second harmonic generation (SHG) capabilities. However, large enhancement in isomorphic Pb-free analogues is rare. Here we report a new NLO material Pb2Ba3(BO3)3Cl with a phase-matching SHG response approximately 3.2× that of KDP and 6× higher than its isomorphic compound Ba5(BO3)3Cl. We show that the enhanced SHG response originates from a unique edge-sharing connection between lead–oxygen polyhedra and boron–oxygen groups, making the dielectric susceptibility more easily affected by the external electric field of an incident photon. This understanding provides a route to identify systems that would benefit from SHG-active cation substitution in isomorphic structures that exhibit weak or null SHG responses.