Two Non-π-Conjugated Deep-UV Nonlinear Optical Sulfates.

The non-π-conjugated sulfate system has long been overlooked as potential deep-UV nonlinear optical (NLO) materials. Here we report two asymmetric anhydrous sulfates, namely, NH4NaLi2(SO4)2 (Ι) and (NH4)2Na3Li9(SO4)7 (Π), which consist of non-π-conjugated [SO4]2- anions. Their single crystals can be readily grown by a facile evaporation method from water solution. Both sulfates are transparent down to the deep-UV region. Interestingly, there is a large NLO gap between I and Π, with phase-matching NLO responses of 1.1 and 0.5 times that of the benchmark KH2PO4, respectively. The first-principles studies reveal that the non-π-conjugated [SO4]2- anions are the dominate NLO-active groups, and the large NLO gap between I and Π can be ascribed to the nonbonding O 2 p orbitals of different orientations in the crystallographically independent S1O4 groups. This work provides an innovative non-π-conjugated source that is distinct from the traditional π-conjugated ones for deep-UV NLO materials.