Breaking the Inherent Interarrangement of [B 3 O 6 ] Clusters for Nonlinear Optics with Orbital Hybridization Enhancement.

The [B 3 O 6 ] group as a prime functional unit provides borates with intrinsic properties that are modified by coordination to cations. Inherent [B 3 O 6 ] cluster structures in borates exclusively made of them have a near-plane configuration, with more than 90% of them having a maximum dihedral angle of zero and the remaining ones being less than 13°. Although such an inherent configuration can produce considerable birefringence for good phase-matching ability, this is not conducive to obtaining high conversion efficiency and beam quality due to the walk-off effects in the nonlinear optical process. In this article, two new borate halides Ca 2 B 3 O 6 X (X = Cl and Br) were reported, in which the confinement effects of distorted halogen-centered secondary building blocks compress the existence space of [B 3 O 6 ] primitives, resulting in the nonparallel arrangement between [B 3 O 6 ] clusters in this series. Both compounds show large second harmonic generation effects, and more importantly, the broken inherent interarrangement of [B 3 O 6 ] clusters makes them a moderate birefringence and small walk-off angle. Their moderate birefringence is due to the large angular alignment between [B 3 O 6 ] clusters, resulting from the orbital hybridization between the Ca s and the O p orbitals of the terminal O atoms on [B 3 O 6 ] clusters. Our model supports this viewpoint and offers guidelines for rearranging [B 3 O 6 ] clusters' arrangements in borates.