2-Pyridinium propanol hydrogen squarate: Experimental and computational study of a nonlinear optical material

Korkmaz U., Bulut A.

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, vol.136, pp.1058-1068, 2015 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 136
  • Publication Date: 2015
  • Doi Number: 10.1016/j.saa.2014.09.130
  • Journal Name: SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1058-1068
  • 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-STRUCTURE, PROTON-TRANSFER, ACID, BETAINE, ANIONS, BOND
  • Ondokuz Mayıs University Affiliated: Yes

Abstract

The experimental and theoretical investigation of a novel organic nonlinear optical (NLO) squarate salt of 2-pyridinium propanol hydrogen squarate (I), C8H12ON+center dot C4HO4-, were reported in this study. The crystal structure of the title compound was found to crystallize in the triclinic P-1 space group. In the asymmetric unit each squaric acid molecules have donated one H atom to the pyridines N1 and N2 atoms of a 2-pyridine propanol molecule, forming the salt (1). The X-ray analysis clearly indicated that the crystal packing has shown the 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 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 are presented and compared with the X-ray analysis result. 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. (C) 2014 Elsevier B.V. All rights reserved.