Rational analysis of hydrogen bonding interaction in phenazine, 2-hydroxynaphthalene (1:1) cocrystal: from molecular modeling to photophysical properties.

Context: Organic cocrystals have a wide range of applications in the field of optics due to their photo responsive property. We present here a newly synthesized phenazine 2-hydroxynaphthalene (1:1) cocrystal, its structural and theoretical calculations which tend to the nonlinear optical property. In the crystal structure of the title cocrystal, the phenazine and 2-hydroxynaphthalene molecules from one- and two-dimensional supramolecular frameworks via O‒H…N hydrogen bonds and C‒H…N, C‒H…π interaction, respectively. The phenazine molecules from an infinite off-set stacking through π…π interaction in the three-dimensional molecular packing of the title cocrystal. The contribution of intermolecular interaction in the three-dimensional molecular packing and the interaction energy calculation is studied by the Hirshfeld surface analysis. The molecular geometry retrieved from the experimental X-ray diffraction analysis is in good agreement with the theoretically calculated parameters. Further, the molecular electrostatic potential (MEP) and frontier molecular orbital (FMO) analysis have been carried out to study the charge distribution and molecular reactive mechanism. Third-order nonlinear optical property of the cocrystals has been analyzed by Z-scan measurements. The determined nonlinear optical absorption coefficient value 6.442 × 10 (m/W) and the nonlinear refractive index value - 5.535 × 10 (m/W) suggest that the crystalline solid can be a good choice of potential nonlinear optical material.

Method: The crystal structures of phenazine 2-hydroxynaphthalene cocrystal was solved by direct methods procedure using SHELXS program and refined by full-matrix least square procedure on F using SHELXL-2018 program on Olex2 software. The computational calculation has been carried out using DFT/B3LYP quantum chemical function with triple zeta 6-311 +  + basis set in the ground state molecular stability using Gaussian 09W program suite. The Hirshfeld surface analysis mapping, associated 2D fingerprint plot, and intermolecular molecular interaction energy calculations were carried out using CrystalExplorer (version 21.5) software.