Open honeycomb frameworks of sulphides AHg4Ga5S12 (A = Rb, Cs) exhibiting infrared nonlinear optical properties
A crystal structure with a diamond-like anionic framework belongs to a non-centrosymmetric macrostructure due to the aligned arrangement of tetrahedral units, meeting the premise of second-order nonlinear optical (NLO) materials. Herein, two new Hg-based sulphides, namely RbHg4Ga5S12 (1) and CsHg4Ga5S12 (2), which are isostructural and crystallise in the trigonal space group R3, are successfully isolated in sealed silica tubes by a solid-state reaction. The features of their three-dimensional open honeycomb frameworks are attributed to the parallel alignment of tetrahedral MS4 (M is disordered by 0.444 Hg and 0.555 Ga) building motifs, accompanied by Rb+ (or Cs+) reseating in the cavities. Notably, although the band gap values of 1 and 2 are 2.30 and 2.36 eV, separately, their thermal expansion anisotropies (0.15 and 0.41, respectively) are favourable for achieving laser-induced damage thresholds (5.6 and 5.8 times that of AgGaS2 for 1 and 2, respectively). In addition, the strong polarisability of tetrahedral MS4 building motifs in the diamond-like anionic structures is responsible for the promising second-harmonic generation (SHG) intensities (1.1 and 1.8 times that of AgGaS2 for 1 and 2, respectively) in the particle size range of 50-75 μm with non-phase-matchable behaviour at 1910 nm. Furthermore, theoretical investigation elaborates that electron transitions in compounds 1 and 2 mainly occur from valence band S-3p to conduction band Hg-6s and Ga-4s states, demonstrating that the linear and nonlinear optical properties originate primarily from the synergy of tetrahedral MS4 units.
| Medienart: |
E-Artikel |
|---|
| Erscheinungsjahr: |
2023 |
|---|---|
| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:52 |
|---|---|
| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 52(2023), 15 vom: 11. Apr., Seite 4873-4879 |
| Sprache: |
Englisch |
|---|
| Beteiligte Personen: |
Lou, Xiao-Yu [VerfasserIn] |
|---|
| Links: |
|---|
| Themen: |
|---|
| Anmerkungen: |
Date Completed 11.04.2023 Date Revised 11.04.2023 published: Electronic Citation Status PubMed-not-MEDLINE |
|---|
| doi: |
10.1039/d2dt03683e |
|---|
| funding: |
|
|---|---|
| Förderinstitution / Projekttitel: |
|
| PPN (Katalog-ID): |
NLM354479075 |
|---|
| LEADER | 01000naa a22002652 4500 | ||
|---|---|---|---|
| 001 | NLM354479075 | ||
| 003 | DE-627 | ||
| 005 | 20231226062317.0 | ||
| 007 | cr uuu---uuuuu | ||
| 008 | 231226s2023 xx |||||o 00| ||eng c | ||
| 024 | 7 | |a 10.1039/d2dt03683e |2 doi | |
| 028 | 5 | 2 | |a pubmed24n1181.xml |
| 035 | |a (DE-627)NLM354479075 | ||
| 035 | |a (NLM)36942557 | ||
| 040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
| 041 | |a eng | ||
| 100 | 1 | |a Lou, Xiao-Yu |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Open honeycomb frameworks of sulphides AHg4Ga5S12 (A = Rb, Cs) exhibiting infrared nonlinear optical properties |
| 264 | 1 | |c 2023 | |
| 336 | |a Text |b txt |2 rdacontent | ||
| 337 | |a ƒaComputermedien |b c |2 rdamedia | ||
| 338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
| 500 | |a Date Completed 11.04.2023 | ||
| 500 | |a Date Revised 11.04.2023 | ||
| 500 | |a published: Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a A crystal structure with a diamond-like anionic framework belongs to a non-centrosymmetric macrostructure due to the aligned arrangement of tetrahedral units, meeting the premise of second-order nonlinear optical (NLO) materials. Herein, two new Hg-based sulphides, namely RbHg4Ga5S12 (1) and CsHg4Ga5S12 (2), which are isostructural and crystallise in the trigonal space group R3, are successfully isolated in sealed silica tubes by a solid-state reaction. The features of their three-dimensional open honeycomb frameworks are attributed to the parallel alignment of tetrahedral MS4 (M is disordered by 0.444 Hg and 0.555 Ga) building motifs, accompanied by Rb+ (or Cs+) reseating in the cavities. Notably, although the band gap values of 1 and 2 are 2.30 and 2.36 eV, separately, their thermal expansion anisotropies (0.15 and 0.41, respectively) are favourable for achieving laser-induced damage thresholds (5.6 and 5.8 times that of AgGaS2 for 1 and 2, respectively). In addition, the strong polarisability of tetrahedral MS4 building motifs in the diamond-like anionic structures is responsible for the promising second-harmonic generation (SHG) intensities (1.1 and 1.8 times that of AgGaS2 for 1 and 2, respectively) in the particle size range of 50-75 μm with non-phase-matchable behaviour at 1910 nm. Furthermore, theoretical investigation elaborates that electron transitions in compounds 1 and 2 mainly occur from valence band S-3p to conduction band Hg-6s and Ga-4s states, demonstrating that the linear and nonlinear optical properties originate primarily from the synergy of tetrahedral MS4 units | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Zhou, Yu |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Wen-Fa |e verfasserin |4 aut | |
| 700 | 1 | |a Jiang, Xiao-Ming |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Bin-Wen |e verfasserin |4 aut | |
| 700 | 1 | |a Guo, Guo-Cong |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Dalton transactions (Cambridge, England : 2003) |d 2004 |g 52(2023), 15 vom: 11. Apr., Seite 4873-4879 |w (DE-627)NLM149339739 |x 1477-9234 |7 nnns |
| 773 | 1 | 8 | |g volume:52 |g year:2023 |g number:15 |g day:11 |g month:04 |g pages:4873-4879 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1039/d2dt03683e |3 Volltext |
| 912 | |a GBV_USEFLAG_A | ||
| 912 | |a GBV_NLM | ||
| 951 | |a AR | ||
| 952 | |d 52 |j 2023 |e 15 |b 11 |c 04 |h 4873-4879 | ||