Fully tricoordinated assembly unveils a pioneering nonlinear optical crystal (SbTeO)(NO)
Balancing the critical property requirements is key to surmounting the obstacles in the application of nonlinear optical (NLO) crystals. Tricoordinated units, characterized by nearly the lowest coordination number, are common in inorganic NLO-active oxides; however, crystals solely composed of such...
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| Published in | Chemical science (Cambridge) Vol. 15; no. 44; pp. 18549 - 18556 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
07.10.2024
The Royal Society of Chemistry |
| Subjects | |
| Online Access | Get full text |
| ISSN | 2041-6520 2041-6539 |
| DOI | 10.1039/d4sc05640j |
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| Summary: | Balancing the critical property requirements is key to surmounting the obstacles in the application of nonlinear optical (NLO) crystals. Tricoordinated units, characterized by nearly the lowest coordination number, are common in inorganic NLO-active oxides; however, crystals solely composed of such units are rare. Herein, by assembling three distinct tricoordinated units (SbO
3
, TeO
3
, and NO
3
) into a single crystal, a pioneering fully tricoordinated NLO material, (SbTeO
3
)(NO
3
), was synthesized
via
a facile volatilization method. As the first reported tellurite-antimonite NLO crystal, (SbTeO
3
)(NO
3
) exhibits well-balanced properties: a strong phase-matched second-harmonic generation (SHG) effect (2.2 × KDP), short UV cutoff edge (253 nm) and moderate birefringence (0.081@546 nm). Unlike most deliquescent nitrates, (SbTeO
3
)(NO
3
) demonstrates exceptional water resistance (>30 days), attributed to its unique hydrophobic layers and stereochemically active lone pair (SCALP) electrons in the Sb
3+
and Te
4+
cations. Theoretical calculations reveal that the optical bandgap and SHG effect of (SbTeO
3
)(NO
3
) are collectively governed by the three tricoordinated motifs, with individual SHG contributions of 20.92%, 23.88%, and 55.12% from [SbO
3
], [TeO
3
] and [NO
3
], respectively. This breakthrough underscores the efficacy of the fully tricoordinated assembly strategy in engineering NLO materials with optimally balanced properties.
Fully tricoordinated assembly yields the first tellurite-antimonite NLO crystal, (SbTeO
3
)(NO
3
), exhibiting well-balanced properties: a strong SHG effect (2.2 × KDP), short UV cutoff edge (253 nm) and moderate birefringence (0.081@546 nm). |
|---|---|
| Bibliography: | Te NO For ESI and crystallographic data in CIF or other electronic format see DOI 3 Electronic supplementary information (ESI) available: Experimental section, computational method, EDS, SEM images and elemental distribution maps, [Sb https://doi.org/10.1039/d4sc05640j 6-MPRs, the 3D structure, TG analysis, PXRD patterns above 1000 °C, structural comparison, crystal data, fractional atomic coordinates and equivalent isotropic displacement parameters, important bond lengths, angles and bond valences, the dipole moments calculation, a summary of reported tellurite nitrate, antimony nitrate and antimony tellurite families and state energies of the H-VB and L-CB of (SbTeO ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/d4sc05640j |