3-Phenylpyridinium hydrogen squarate: Experimental and computational study of a nonlinear optical material

Korkmaz U., Bulut A., Bulut I.

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, vol.140, pp.140-149, 2015 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 140
  • Publication Date: 2015
  • Doi Number: 10.1016/j.saa.2014.12.029
  • Journal Name: SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.140-149
  • Keywords: Squaric acid, X-ray diffraction, Strong hydrogen bonding, Vibrational spectra, Quantum chemical calculations, Non-linear optical materials, DENSITY-FUNCTIONAL THEORY, X-RAY-DIFFRACTION, VIBRATIONAL-SPECTRA, MOLECULAR-STRUCTURE, CRYSTAL-STRUCTURES, PROTON-TRANSFER, SOLID-STATE, ACID, BOND, BETAINE
  • Ondokuz Mayıs University Affiliated: Yes

Abstract

The detailed investigation of an organic nonlinear optical (NLO) squarate salt of 3-phenylpyridinium hydrogen squarate (1), C11H10N+center dot C4HO4-, was reported in this study. The XRD data indicates that the crystal structure of the title compound is in the triclinic P-1 space group. In the asymmetric unit, the 3-phenylpyridine molecule is protonated by one hydrogen atom donation of squaric acid molecule, forming the salt (1). The X-ray analysis shows that the crystal packing has hydrogen bonding ring pattern of D-2(2)(10) (alpha-dimer) through N--H center dot center dot center dot O interactions. The structural and vibrational properties of the compound were also studied by computational methods of ab initio at DFT/B3LYP/6-31++G(d,p) (2) and HF/6-31++G(d,p) (3) levels of theory. The calculation results on the basis of two models for both the optimized molecular structure and vibrational properties for the 1 are presented and compared with the experimental results. Non-linear optical properties (NLO) of the title compound together with the molecular electrostatic potential (MEP), electronic absorption spectrum, frontier molecular orbitals (FMOs) and conformational flexibility were also studied at the 2 level and the results were reported. In order to evaluate the suitability for NLO applications thermal analysis (TG, DTA and DTG) data of 1 were also obtained. (C) 2014 Elsevier B.V. All rights reserved.