Laib Assia, Elhorri Abdelkader M, Hedidi Madani, Zouaoui-Rabah Mourad, Mahdjoub-Araibi Hicham, Zenati Mahammed
Laboratory of Materials Chemistry Catalysis and Reactivity, Department of Chemistry, Faculty of Exact Sciences and Informatics, Hassiba Benbouali University of Chlef, Ouled Fares Chlef, P.O. Box 78C, 02180, Chlef, Algeria.
Departement of Chemistry, Faculty of Exact Sciences and Informatics, Hassiba Benbouali University of Chlef, Ouled Fares Chlef, P.O. Box 78C, 02180, Chlef, Algeria.
J Mol Model. 2025 Feb 28;31(3):101. doi: 10.1007/s00894-025-06326-7.
This research focuses on the theoretical study of six push-pull molecules composed of conjugated bridges based on porphyrin and metalloporphyrins where the metals used are Fe(II), Co(II), Ni(II), Cu(II), and Zn(II); these bridges are linked at their ends by acceptor groups (-NO) and donors (-N(CH)) at the meso positions of the cycles mentioned before. The CAM-B3LYP, M08HX, and MN15 functionals tend to describe well the systems studied in non-linear optics NLO in addition to the use of the basis set 6-31 + + G(d,p) which is considered to be the adequate and least expensive basis set. The highest values of the first static hyperpolarizabilities (β) are assigned to the two molecules 2A and 3A; the corresponding values are as follows: β (2A) = 46.43 * 10 esu and β (3A) = 46.30 * 10 esu. The highest value of the second static hyperpolarizability (γ) is assigned to the molecule 1A5 with a value of 9.49 * 10 esu. The highest values of the first dynamic hyperpolarizabilities ( ) and second dynamics hyperpolarizabilities ( ) are attributed to the molecule 2A; the corresponding values are as follows: ) (2A) = 8229.88 * 10 esu and (2A) = - 10,943.10 * 10 esu. The molecules 1A2 and 1A5 based on the metals Co(II) and Zn(II), respectively, are the most profitable in second- and third-order dynamic NLOs. The specific solvents for the six molecules are acetone, acetonitrile, and dichloromethane. The maximum wavelengths recorded for all molecules in vacuum and in combination with all solvents are in the range 355.75 to 397.15 nm and absorb in the UV transparency.
All calculations were performed with the Gaussian 16 program. The dispersion functional B3LYP-D3 is used for optimizations. Electronic parameters were calculated using the following functionals: CAM-B3LYP, LC-wPBE, LC-BLYP, M11, wB97X, M08-HX, M06-2X, MN12SX, and MN15. The basis set studied for the whole manuscript is 6-31 + + G(d,p) for non-metallic atoms and LanL2DZ for transition metals. Other basis sets studied include 6-31G(d,p), 6-31 + + G(d,p), cc-pVDZ, AUG-cc-pVDZ, 6-311G(d,p), 6-311 + + G(d,p), cc-pVTZ, and AUG-cc-pVTZ. The natural bond orbital (NBO) method was also considered. The implicit solvation models studied are solvation models based on density (SMD) and conductor polarizable continuum model (C-PCM). The time-dependent density functional (TD-DFT) approach was also studied.
本研究聚焦于六种由基于卟啉和金属卟啉的共轭桥组成的推挽分子的理论研究，其中所使用的金属为Fe(II)、Co(II)、Ni(II)、Cu(II)和Zn(II)；这些桥在其末端通过之前提到的环的中位上的受体基团(-NO)和供体基团(-N(CH))相连。除了使用被认为是合适且成本最低的基组6-31++G(d,p)之外，CAM-B3LYP、M08HX和MN15泛函倾向于很好地描述非线性光学（NLO）中所研究的体系。第一静态超极化率(β)的最高值被赋予两个分子2A和3A；相应的值如下：β(2A)=46.43×10 esu且β(3A)=46.30×10 esu。第二静态超极化率(γ)的最高值被赋予分子1A5，其值为9.49×10 esu。第一动态超极化率( )和第二动态超极化率( )的最高值归因于分子2A；相应的值如下： )(2A)=8229.88×10 esu且 (2A)= - 10,943.10×10 esu。分别基于金属Co(II)和Zn(II)的分子1A2和1A5在二阶和三阶动态NLO中最具优势。这六种分子的特定溶剂为丙酮、乙腈和二氯甲烷。在真空以及与所有溶剂组合的情况下，所有分子记录的最大波长在355.75至397.15 nm范围内，并在紫外透明区吸收。
所有计算均使用高斯16程序进行。色散泛函B3LYP-D3用于优化。使用以下泛函计算电子参数：CAM-B3LYP、LC-wPBE、LC-BLYP、M11、wB97X、M08-HX、M06-2X、MN12SX和MN15。整个手稿所研究的基组对于非金属原子为6-31++G(d,p)，对于过渡金属为LanL2DZ。所研究的其他基组包括6-31G(d,p)、6-31++G(d,p)、cc-pVDZ、AUG-cc-pVDZ、6-311G(d,p)、6-311++G(d,p)、cc-pVTZ和AUG-cc-pVTZ。还考虑了自然键轨道（NBO）方法。所研究的隐式溶剂化模型是基于密度的溶剂化模型（SMD）和导体极化连续介质模型（C-PCM）。还研究了含时密度泛函（TD-DFT）方法。
