Ba(MoO2F)2(XO3)2 (X = Se and Te): First Cases of Noncentrosymmetric Fluorinated Molybdenum Oxide Selenite/Tellurite Through Unary Substitution for Enlarging Band Gaps and Second Harmonic Generation

Nonlinear optical (NLO) materials have critically important applications in advanced laser technologies. However, achieving a good balance between the mutual competing NLO properties and band gap within one molecular structure remains a great challenge. In this study, two alkaline earth metal fluorinated molybdenum oxide selenite/tellurite, Ba(MoO 2 F) 2 (XO 3 ) 2 [X = Se (BMFS) and Te (BMFT)], were synthesized through a facile unary substitution: BMFS was obtained by partial substitution of oxygen atoms with highly electronegative fluorine in the parent compound BaMo 2 O 5 (SeO 3 ) 2 (BMS), while BMFT was achieved by further replacing lone-pair Se 4+ cations in BMFS with heavier Te 4+ cations in the same main group. By partially replacing oxygen with fluorine, BMFS shows a broadened band gap and enhanced second harmonic generation (SHG) response compared to BMS owing to the high electronegativity of fluorine anions and the favorable orientation and alignment of NLO-active [MoO 5 F] 5- and [SeO 3 ] 2- groups, which is relatively rare for unary anion substitution. BMFS and BMFT are isostructural and both belong to the polar space group Aba 2, featuring a three-dimensional (3D) double-layered framework composed of 2D [MoO 4 F(XO 3 )] ∞ anionic layers interconnected by divalent barium cations. Both BMFS and BMFT exhibit good optical performance, including large SHG responses (3× and 4× KH 2 PO 4 ), wide band gaps (3.30 and 3.27 eV) and optical transparency window, and high laser damage thresholds (60× and 53× AgGaS 2 ), demonstrating their potential applications as promising second-order NLO crystals. DFT calculations have elucidated the crucial role of the [MoO 5 F] 5- groups in the enlarged band gaps and enhanced SHG responses in BMFS and BMFT. This work proposes a feasible unary substitution strategy for synthesizing the first polar fluorinated molybdenum oxide selenite/tellurite with synchronously enlarged band gaps and SHG efficiency.