Synthesis, an experimental and quantum chemical computational study of a new nonlinear optical material: 2-Picolinium hydrogensquarate

摘要

The experimental and theoretical investigation results of a novel organic non-linear optical (NLO) organic squarate salt of 2-Picolinium hydrogensquarate (1), C_6H_8N~+ · C_4HO_4~-, were reported in this study. The space group of the title compound was found in the monoclinic C2/c space group. It was found that the asymmetric unit consists of one monohydrogen squarate anion together with mono protonated 2-Picolinium, forming the (1) salt. The X-ray analysis clearly indicated that the crystal packing has shown the hydrogen bonding ring pattern of D_2~2(10) (α-dimer) through N-H…O interactions. The hydrogensquarate anions form a-dimer, while 2-Picolinium molecule interacts through N-H…O and C-H…O with the hydrogensquarate anion. The structural and vibrational properties of the compound were also studied by computational methods of ab initio performed on the compound at DFT/B3LYP/6-31++G(d,p) (2) and HF/6-31++G(d,p) (3) level of theory. The calculation results on the basis of two models for both the optimized molecular structure and vibrational properties for the 1 obtained are presented and compared with the X-ray analysis result. On the other the molecular electrostatic potential (MEP), electronic absorption spectra, frontier molecular orbitals (FMOs), conformational flexibility and non-linear optical properties (NLO) of the title compound were also studied at the 2 level and the results are reported. In order to evaluate the suitability for NLO applications thermal analysis (TG, DTA and DTG) data of 1 were also obtained.