Synthesis, structural characterization and computational study of a novel amino chalcone: a potential nonlinear optical material. (26th January 2017)

• Record Type: Journal Article
• Authors: Almeida, Leonardo R.; Anjos, Murilo M.; Ribeiro, Gabriela C.; Valverde, Clodoaldo; Machado, Daniel F. S.; Oliveira, Guilherme R.; Napolitano, Hamilton B.; de Oliveira, Heibbe C. B.
• Is Part Of: New journal of chemistry. Volume 41:Number 4(2017)
• Page Start: 1744
• Page End: 1754
• Publication Date: 2017-01-26
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c5nj03214h
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : The interest for novel chalcone-based materials in nonlinear optics is dependent on strong second harmonic generation in organic systems. Abstract : The interest for novel chalcone-based materials in nonlinear optics is dependent on strong second harmonic generation in organic systems. Chalcones are α, β-unsaturated ketones that can be easily obtained by Claisen–Schmidt condensation between ketones and aromatic aldehydes. A new 2-amino-chalcone was synthesized and its crystal molecular structure was elucidated using the single crystal X-ray diffraction technique. This compound, C15 H12 BrNO2, crystallizes in monoclinic centrosymmetric space group C 2/ c with cell parameters a = 29.47(7) Å; b = 6.97(5) Å, c = 13.59(1) Å, β = 112.52(6)° and V = 2581.2(2) Å 3 . In addition to the crystal structure, the analysis of Hirshfeld surfaces indicates the presence of hydrogen bonds of types N–H⋯O and O–H⋯O that stabilize two independent centrosymmetric dimers, and also indicates the presence of π–π stacking interactions that stabilize a supramolecular trimeric system. Being a push–pull chromophore we investigated the NLO properties of the 2-amino-chalcone asymmetric unit using the supermolecule approach in combination with an iterative electrostatic polarization scheme. The calculations were performed using the CAM-B3LYP/6-311+G(d) level of theory for both dynamic and static situations. In the presence of the embedding charges, the γ value is increased by 20% for the dynamic calculation but only 8% for the static limit. In contrast to the crystal form, when in solution the 2-amino-chalcone lacks an inversion center so that second order NLO properties do not vanish. Following this idea we computed the NLO properties using the implicit solvation approach IEF-PCM. The solvent effect on the NLO properties was to augment its values as the solvent polarity increases. We obtained for the in-crystal and in DMSO 2-amino-chalcone, γ (−2 ω ; ω, ω, 0) = 144.12 × 10 −36 esu and 260.163 × 10 −36 esu, respectively, and therefore interesting materials for third order NLO applications.