NaMoO3(IO3)(H2O): water molecule introduction induces strong second harmonic generation response, widened band gap and large anisotropy

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 3; pp. 1221 - 1229
• Main Authors: Yi Shui, Liang, Zhengli, Li, Zhenhua, Wan, Jiahao, Liu, Lehui, Jiang, Xingxing, Lin, Zheshuai, Liu, Hongming
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 16.01.2024
• Subjects: Anisotropy; Birefringence; Chemical bonds; Energy gap; Feasibility studies; Hydrogen bonds; Molecular structure; Nonlinear optics; Potassium phosphates; Second harmonic generation; Water chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d3dt03304j

Exploring feasible tactics to induce the formation of non-centrosymmetric (NCS) structures, especially from centrosymmetric (CS) structures, is essential for the development of nonlinear optical crystals with more potential. An NCS alkali metal-containing molybdenum iodate hydrate, namely, NaMoO3(IO3)(H2O), was designed based on the CS matrix NaMoO3(IO3) via introducing a water molecule into the structure. The introduction of one crystalline water molecule results in the rearrangement of Λ-shaped cis-[MoO4(IO3)2] units, and the proper array of the cis-[MoO4(IO3)2] units in NaMoO3(IO3)(H2O) results in its strong SHG response of 4.6 × KH2PO4. In addition, NaMoO3(IO3)(H2O) exhibits a wider optical bandgap of 3.44 eV and a larger birefringence of 0.231 than its matrix. Furthermore, the framework of NaMoO3(IO3)(H2O) is highly similar to that of α-KMoO3(IO3), with water molecules assisting Na+ cations in occupying the position of K+. However, due to the extra hydrogen bond of water molecules, the [MoO3(IO3)]∞ layers in NaMoO3(IO3)(H2O) retain a parallel-stacking arrangement, different from the antiparallel arrangement of layers in α-KMoO3(IO3) with a centric structure. This study confirms the feasibility of applying a water molecule to adjust the orientation of basic building block units to assemble an NCS structure based on CS crystals.