Sundareswaran T, Jagan R, Karthikeyan N, Boaz B Milton
Department of Science and Humanities, R.M.K. College of Engineering and Technology, Puduvoyal, Tamil Nadu, 601206, India.
Department of Physics, Presidency College, Chennai, Tamil Nadu, 600005, India.
J Mol Model. 2024 Sep 27;30(10):351. doi: 10.1007/s00894-024-06128-3.
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.
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.
有机共晶体因其光响应特性在光学领域有广泛应用。我们在此展示一种新合成的吩嗪 - 2 - 羟基萘（1:1）共晶体，其结构及理论计算倾向于非线性光学性质。在该标题共晶体的晶体结构中，吩嗪和2 - 羟基萘分子分别通过O‒H…N氢键和C‒H…N、C‒H…π相互作用形成一维和二维超分子框架。在标题共晶体的三维分子堆积中，吩嗪分子通过π…π相互作用形成无限的错位堆积。通过Hirshfeld表面分析研究了三维分子堆积中分子间相互作用的贡献及相互作用能计算。从实验X射线衍射分析获得的分子几何结构与理论计算参数吻合良好。此外，还进行了分子静电势（MEP）和前线分子轨道（FMO）分析以研究电荷分布和分子反应机理。通过Z - 扫描测量分析了共晶体的三阶非线性光学性质。所确定的非线性光学吸收系数值6.442×10（m/W）和非线性折射率值 - 5.535×10（m/W）表明该晶体固体可能是潜在非线性光学材料的良好选择。
使用SHELXS程序通过直接法程序解析吩嗪 - 2 - 羟基萘共晶体的晶体结构，并在Olex2软件上使用SHELXL - 2018程序对F进行全矩阵最小二乘法精修。使用高斯09W程序套件，采用DFT/B3LYP量子化学函数和三重ζ 6 - 311++基组在基态分子稳定性方面进行计算。使用CrystalExplorer（版本21.5）软件进行Hirshfeld表面分析映射、相关的二维指纹图谱和分子间相互作用能计算。
