Rb₃VO(O₂)₂CO₃: A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

Abstract

A nonlinear optical (NLO) carbonatoperoxovanadate, Rb3VO(O2)2CO3, was synthesized through a simple solution‐evaporation method in phase‐pure form. Single‐crystal X‐ray diffraction revealed that the structure of Rb3VO(O2)2CO3 consists of important noncentrosymmetric (NCS) chromophores, that is, π‐delocalized (CO3)2− groups, a second‐order Jahn–Teller (SOJT) distortive V5+ cation, and π‐localized distorted O22− groups, as well as charge‐balancing polarizable Rb+ ions. The powder second‐harmonic generation (SHG) measurements indicated that Rb3VO(O2)2CO3 is phase‐matchable (Type I) and exhibits a remarkably strong SHG response circa 21.0 times that of potassium dihydrogen phosphate (KDP), which is the largest efficiency observed among carbonate NLO materials. First‐principles calculation analysis suggests that the extremely large SHG response of Rb3VO(O2)2CO3 is attributed to the synergistic effect of the cooperation of all the constituting NCS chromophores.

From Centrosymmetry to Noncentrosymmetry: Tailoring the Structural Arrangements of Carbonates with Strong Nonlinear Optical Response through Partial Anion Substitution

“…[ 15 ] Among them, carbonates with planar triangular π‐conjugated (CO 3 ) 2− groups play an unignorable role in NLO materials because the perfectly organized (CO 3 ) 2− group is beneficial for large SHG polarizability to improve laser conversion efficiency and moderate birefringence to realize phase‐matching (PM). [ 16 ] In recent years, several carbonates have been reported as UV and even deep‐UV NLO crystals such as LiNaCO 3 , [ 17 ] NaZnCO 3 (OH), [ 13b ] MNCO 3 F (M = Na/K/Rb/Cs; M = Mg/Ca/Sr/Zn/Cd/Ge/Sn/Pb), [ 18 ] Na 3 Ln(CO 3 ) 3 (Ln = Y/Gd), [ 19 ] Ln 8 O(CO 3 ) 3 (OH) 15 X (Ln = Y/Lu, X = Cl/Br), [ 20 ] etc. To date, some strategies have been adopted for carbonate NLO crystals with intriguing properties: [ 21 ] 1) Total cation substitution method.…”

“…Apart from mentioned borate crystals, there are many NLO crystal systems containing other π‐conjugated groups, such as carbonates, [ 13 ] nitrates, [ 14 ] and the emerging cyanurates. [ 15 ] Among them, carbonates with planar triangular π‐conjugated (CO 3 ) 2− groups play an unignorable role in NLO materials because the perfectly organized (CO 3 ) 2− group is beneficial for large SHG polarizability to improve laser conversion efficiency and moderate birefringence to realize phase‐matching (PM).…”

THEORETICAL STUDY OF THE BONDING BETWEEN ALGINATE AND GRAPHENE OXIDE THROUGH THE INTERACTION OF ITS CARBOXYLIC GROUPS WITH THE DIVALENT METALS Cu2+, Co2+, Zn2+, AND Mn2+

“…In this case, it can be related to the electron density found around the bonding region (blue color) with ELF values close to 0.5 (fermi gas reference value), which indicates a high degree of electronic delocalization (28; 44). In the case of O77, its non-bonding pairs are seen to be more localized and homogeneously distributed, indicating little interaction with the metal (43) These results are also related to the low values of 𝐸 (2) , obtained in the analysis of natural bonding orbitals. The attractor analysis shows that the interactions between O76 and O100 with copper are the most important.…”