Mahdjoub-Araibi Hicham, Zouaoui-Rabah Mourad, Hedidi Madani, Elhorri Abdelkader M, Laib Assia, Zenati Mohammed
Laboratory of Materials Chemistry Catalysis and Reactivity, Department of Chemistry, Faculty of Exact Sciences and Informatics, Hassiba BenBouali University, P.O. Box 78C, 02180, Ouled Fares, Chlef, Algeria.
Departement of Chemistry, Faculty of Exact Sciences and Informatics, Hassiba BenBouali University, P.O. Box 78C, 02180, Ouled Fares, Chlef, Algeria.
J Mol Model. 2025 Feb 3;31(3):73. doi: 10.1007/s00894-025-06294-y.
This research is based on the theoretical study of seven push-pull molecules composed of conjugated bridges based on two different organometallic rings, these bridges are linked at their ends by acceptor groups (-NO) and donor groups (-N(CH)) on the α position of the rings mentioned above. The location of the donor and acceptor groups revealed that the addition of the acceptor groups near the rings (Titanol, Ferrol and Nickelol) improves the NLO response in comparison with the grafting of these groups on the Zinkol ring and also influences the positioning of the π electrons at the level of the chromophores studied. The molecule 2B gave the highest values of static first hyperpolarisabilitiy (β) and static second hyperpolarisabilitiy (γ), knowing that: β (2B) = 135.79 * 10 esu and γ (2B) = 135.79 * 10 esu. The highest values of dynamic first and second hyperpolarisabilities are assigned to the molecule 1C with the following values: =1,218,310.00 * 10 esu and =1,324,520,000 * 10 esu. The metal Zn is considered as an acceptor group and the remaining metals (Ti, Fe and Ni) are considered as donor groups. The specific solvents for the seven molecules are water, ethanol and acetonitrile. The maximum wavelengths recorded for all molecules in combination with all solvents are in the range of 421.39 to 765.28 nm. λ METHOD: The calculations were performed using Gaussian 16 software to perform DFT calculations with B3LYP functional. The LanL2DZ basis-set was used for transition metals, while the 6-31 + + G(d,p) basis-set was used for nonmetal atoms. The functionals used are: CAM-B3LYP, LC-wPBE, LC-BLYP, M11, wB97X, M08-HX, M06-2X, MN12SX, MN15, and M06HF. The basis-sets used are: 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) calculations are performed by the NBO program incorporated by default in the Gaussian 16 program. The solvation models studied are the CPCM model (conductor polarizable continuum model) and the SMD model (Solvation Model Density). Excited states calculations are calculated by the time-dependent DFT method (TD-DFT).
本研究基于对七种由基于两种不同有机金属环的共轭桥组成的推拉分子的理论研究，这些桥在其末端通过上述环α位上的受体基团（-NO）和供体基团（-N(CH)）相连。供体和受体基团的位置表明，与在锌环上接枝这些基团相比，在环（钛环、铁环和镍环）附近添加受体基团可改善非线性光学响应，并且还会影响所研究发色团水平上π电子的定位。分子2B给出了静态第一超极化率（β）和静态第二超极化率（γ）的最高值，已知：β(2B) = 135.79×10 esu且γ(2B) = 135.79×10 esu。动态第一和第二超极化率的最高值归属于分子1C，其值如下： = 1,218,310.00×10 esu和 = 1,324,520,000×10 esu。金属锌被视为受体基团，其余金属（钛、铁和镍）被视为供体基团。这七种分子的特定溶剂为水、乙醇和乙腈。所有分子与所有溶剂组合记录的最大波长在421.39至765.28 nm范围内。λ方法：使用高斯16软件进行计算，以使用B3LYP泛函执行密度泛函理论（DFT）计算。LanL2DZ基组用于过渡金属，而6 - 31++G(d,p)基组用于非金属原子。所使用的泛函有：CAM - B3LYP、LC - wPBE、LC - BLYP、M11、wB97X、M08 - HX、M06 - 2X、MN12SX、MN15和M06HF。所使用的基组有：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。自然键轨道（NBO）计算由高斯16程序中默认包含的NBO程序执行。所研究的溶剂化模型是导体极化连续介质模型（CPCM模型）和溶剂化模型密度（SMD模型）。激发态计算通过含时密度泛函理论方法（TD - DFT）进行。
