BaCa(BO)F: π-conjugation of BO in the planar pentagonal layer achieving large second harmonic generation of -borate.

The nonlinear optical (NLO) crystals that can expand the wavelength of the laser to the deep-ultraviolet (DUV) region by the cascaded second harmonic generation (SHG) are of current research interest. It is well known that borates are the most ideal material class for the design of new DUV NLO crystals owing to the presence of good NLO genes, , BO or BO groups. However, the NLO -borates with the BO dimers as the sole basic building units are still rarely reported owing to their small SHG responses. In this communication, by constructing a planar pentagonal [Ca(BO)] layer, the NLO -borate BaCa(BO)F with a large SHG response (∼2.2 × KDP, or ∼7 × α-LiBO) and a DUV transparent window has been designed and synthesized. The first-principles calculations show that the large SHG response of BaCa(BO)F mainly originates from the better π-conjugation of the coplanar BO dimers in the [Ca(BO)] layer. In addition, the planar pentagonal pattern in the [Ca(BO)] layer provides an ideal template for designing the new DUV NLO crystals, apart from those in known DUV borates, , the [BeBOF] layer in KBeBOF (KBBF).