Discovery of NLO Semiorganic (C5H6ON)+(H2PO4)-: Dipole Moment Modulation and Superior Synergy in Solar-Blind UV Regions

We herein report a novel semiorganic NLO material, (C5H6ON)(+)(H2PO4)(-), 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(+), (C5H6ON)(+)) 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 degrees C of LAP); wider transparency range (0.26-1.50 mu m); very strong SHG response (3 x KDP); a suitable large birefringence (Delta n(cal) = 0.25 vs 0.075 of LAP); and a high laser-induced damage threshold (2.2 x KDP). First-principles calculations show that the pi-conjugated organic (4HP)(+) 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.

Automated summary

A novel semiorganic NLO material, 4HPP, has been reported with excellent properties surpassing the commercialized LAP, including better thermal stability, a wider transparency range, stronger SHG response, and a higher laser-induced damage threshold. The study highlights the importance of the π-conjugated organic cation and synergy of organic and inorganic moieties in governing the optical anisotropy and SHG process, respectively. This discovery paves the way for the rational design of high-performance semiorganic materials with acentric structures.