Abstract In this study, special attention has been paid to understanding the structural effect on electronic structure, absorption spectra and nonlinear optical (NLO) response for a series of heteroleptic diimine dithiolate complexes [M(bpy)(bdt)] (M = Ni, Pd and Pt; bpy = 2,2′-bipyridine, bdt = 1,2-benzenedithiolate) attached to BODIPY and amido-BODIPY dyes through density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. Natural bond orbital (NBO) analyses are also performed for scrutinizing the structural properties of the considered heteroleptic complexes. The calculated energy gaps show that the substitution of BODIPY or amido-BODIPY groups on the diimine ligand (bpy) leads to reduce of HLG. In contrast, these substitutions on the dithiolate ligand (bdt) are slightly increased energy gap. Moreover, the entitled substitutions at the diimine position can be red-shifted, and the expansion of absorption range to the near-IR region. It is interesting to note that the BODIPY and amido-BODIPY substitutions dramatically increase the static first hyperpolarizability (β0) value. The results suggest that structural modifications on the diimine and dithiolate ligands using BODIPY and amido-BODIPY dyes can finely tune their linear and nonlinear optical properties.

中文翻译：

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探索具有 BODIPY 和酰胺基-BODIPY 取代的杂配配合物的光学和非线性光学特征；比较理论研究

摘要 在这项研究中，特别关注了解一系列杂配二亚胺二硫醇配合物 [M(bpy)(bdt)] (M = Ni, Pd 和 Pt；bpy = 2,2'-联吡啶，bdt = 1,2-苯二硫醇盐）通过密度泛函理论 (DFT) 和时间相关密度泛函理论 (TD-DFT) 方法连接到 BODIPY 和酰胺基-BODIPY 染料。还进行了自然键轨道 (NBO) 分析，以检查所考虑的杂配复合物的结构特性。计算出的能隙表明，二亚胺配体 (bpy) 上的 BODIPY 或酰胺基-BODIPY 基团的取代导致 HLG 的减少。相比之下，二硫醇配体 (bdt) 上的这些取代是略微增加的能隙。而且，二亚胺位置的标题取代可以红移，吸收范围扩大到近红外区域。有趣的是，BODIPY 和酰胺基-BODIPY 取代显着增加了静态第一超极化 (β0) 值。结果表明，使用 BODIPY 和酰胺基 BODIPY 染料对二亚胺和二硫醇配体进行结构修饰可以微调它们的线性和非线性光学特性。