Synthesis, crystal structure and solid-state properties of 4-(3-nitrophenylamino)-4-methylpentan-2-one picrate (3NAP): An efficient cocrystal for chi((3)) optics

摘要

An organic 4-(3-nitrophenylamino)-4-methylpentan-2-one picrate (3NAP) cocrystal was synthesized using slow solvent evaporation technique and its crystal structure is reported. The 3NAP compound crystallized in monoclinic crystal system with centrosymmetric space group P2(1)/c and the cell parameters are found to be a=8.6339 angstrom, b=19.1965 angstrom, c=13.2058 angstrom, alpha=90 degrees, beta=106.725 degrees, gamma=90 degrees and V=2096.1 angstrom(3). Best agreement between theoretical and experimental value of CHN elemental composition confirmed inclusionless compound formation. The reasonable FWHM value of prominent peak observed from high-resolution X-ray diffraction experiment indicates superior crystallinity of 3NAP. The load-dependent hardness values measured at (010), (010), and (001) - planes of 3NAP single crystal admit its mechanical anisotropy. Further, the work hardening coefficient confirms that the title crystal belongs to the soft material category. The dark and photocurrent of the 3NAP crystal were measured, and it exhibits positive photoconductivity. The laser-induced surface damage threshold of the 3NAP crystal was found to be 7.5 GWcm(-2). Nonlinear coupling between the intermolecular charge transfer and an applied optical field enhanced third order nonlinear optical properties. The intermolecular charge transfer and interactions are proved to be true in 3NAP via Hirshfeld surface analysis. The third order nonlinear optical susceptibility (chi((3))) and optical limiting threshold under continuous-wave laser excitation was measured to be 3.96 x 10(-6) esu and 3.44 x 10(3) Wcm(-2). The superior physicochemical and nonlinear optical properties promote the title material as a promising candidate for nonlinear optical device applications. (C) 2020 Elsevier B.V. All rights reserved.