NaMoO(IO)(HO): water molecule introduction induces strong second harmonic generation response, widened band gap and large anisotropy
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, NaMoO 3 (...
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| Published in | Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 3; pp. 1221 - 1229 |
|---|---|
| Main Authors | , , , , , , , |
| Format | Journal Article |
| Published |
16.01.2024
|
| Online Access | Get full text |
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| Summary: | 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, NaMoO
3
(IO
3
)(H
2
O), was designed based on the CS matrix NaMoO
3
(IO
3
)
via
introducing a water molecule into the structure. The introduction of one crystalline water molecule results in the rearrangement of Λ-shaped
cis
-[MoO
4
(IO
3
)
2
] units, and the proper array of the
cis
-[MoO
4
(IO
3
)
2
] units in NaMoO
3
(IO
3
)(H
2
O) results in its strong SHG response of 4.6 × KH
2
PO
4
. In addition, NaMoO
3
(IO
3
)(H
2
O) exhibits a wider optical bandgap of 3.44 eV and a larger birefringence of 0.231 than its matrix. Furthermore, the framework of NaMoO
3
(IO
3
)(H
2
O) is highly similar to that of α-KMoO
3
(IO
3
), with water molecules assisting Na
+
cations in occupying the position of K
+
. However, due to the extra hydrogen bond of water molecules, the [MoO
3
(IO
3
)]
∞
layers in NaMoO
3
(IO
3
)(H
2
O) retain a parallel-stacking arrangement, different from the antiparallel arrangement of layers in α-KMoO
3
(IO
3
) 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.
A new acentric iodate, NaMoO
3
(IO
3
)(H
2
O), was obtained by introducing a water molecule into a centrosymmetric matrix, which induced the reorientation of Λ-shaped [MoO
4
(IO
3
)
2
] units and a strong nonlinear effect. |
|---|---|
| Bibliography: | For ESI and crystallographic data in CIF or other electronic format see DOI https://doi.org/10.1039/d3dt03304j 2296933 Electronic supplementary information (ESI) available: Crystallographic data, dipole moment calculation, SHG coefficients, XRD patterns, EDS, additional crystal structure, IR spectrum, TGA curves, XRD of residue. CCDC |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/d3dt03304j |