Back to Search
Start Over
Discovery of NLO Semiorganic (C 5 H 6 ON) + (H 2 PO 4 ) - : Dipole Moment Modulation and Superior Synergy in Solar-Blind UV Region.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2021 Mar 10; Vol. 143 (9), pp. 3647-3654. Date of Electronic Publication: 2021 Mar 01. - Publication Year :
- 2021
-
Abstract
- We herein report a novel semiorganic NLO material, (C <subscript>5</subscript> H <subscript>6</subscript> ON) <superscript>+</superscript> (H <subscript>2</subscript> PO <subscript>4</subscript> ) <superscript>-</superscript> , 4HPP, showing promising excellent properties in the important solar-blind UV region where LAP and its deuterated form DLAP are the only commercialized semiorganic materials. For the first time, the 4-hydroxypyridine (4HP <superscript>+</superscript> , (C <subscript>5</subscript> H <subscript>6</subscript> ON) <superscript>+</superscript> ) cation is identified as NLO active and how to eliminate the dipole-dipole interaction to avoid the unwanted center-symmetry-trap caused by the polar-induced susceptibility is well demonstrated. Remarkably, 4HPP exhibits competitive and even better properties compared with LAP that include better thermal stability (decomposition at 166 vs 112 °C of LAP); wider transparency range (0.26-1.50 μm); very strong SHG response (3 × KDP); a suitable large birefringence (Δ n <subscript>cal</subscript> = 0.25 vs 0.075 of LAP); and a high laser-induced damage threshold (2.2 × KDP). First-principles calculations show that the π-conjugated organic (4HP) <superscript>+</superscript> cation governs the optical anisotropy, whereas the synergy of the organic and inorganic moieties dominates the SHG process. Our discovery points out a new path for the rational design of high performance semiorganic materials that require an acentric structure.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 143
- Issue :
- 9
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 33646792
- Full Text :
- https://doi.org/10.1021/jacs.1c00959