Dyestuff Technology Department, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai 400019, Maharashtra, India.
Dyestuff Technology Department, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai 400019, Maharashtra, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2020 Jan 5;224:117421. doi: 10.1016/j.saa.2019.117421. Epub 2019 Jul 29.
Novel Donor (D)-π-Acceptor (A) NLOphoric triphenylamine-imidazole based dye 9 was designed, synthesized, and confirmed by Mass, C NMR, and H NMR analysis. Photophysical properties of 9 were studied in solvents of different polarities and compared with analogues compounds 7 and 8. Phenonthroline acceptor based dye 9 shows highly bathochromic shifted absorption and emission compared to dyes 7 and 8. Positive solvatochromism was noticed in 7, 8, and 9 which was supported by the linear (i.e. Lippert-Mataga and Mac-Rae polarity functions) and multi-linear (i.e. Kamlet-Taft and Catalan parameters) analysis. Moreover, solvent polarizability (d) and solvent dipolarity (C) are the major factors responsible for red shift in absorption as well as in emission spectra. Charge transfer descriptors as well as the polarity graphs are in good relation with Generalized Mulliken-Hush (GMH) parameters. NLO properties of 7, 8, and 9 were studied by using solvatochromic and computational methods. The static first hyperpolarizability (β) and relevant microscopic parameters (μ,α,α,β,γ) were determined using DFT with B3LYP, BHHLYP, and CAM-B3LYP functionals. Third-order NLO properties of nitrogen containing phenanthroline based compound 9 were observed to be several times higher than those of the compounds 7 and 8, justify the design approach.
新型供体（D）-π-受体（A） NLOphoric 三苯胺-咪唑基染料 9 被设计、合成，并通过质谱、C NMR 和 H NMR 分析得到证实。研究了 9 在不同极性溶剂中的光物理性质，并与类似物化合物 7 和 8 进行了比较。与染料 7 和 8 相比，基于 phenonthroline 受体的染料 9 表现出明显的红移吸收和发射。在 7、8 和 9 中观察到正溶剂化变色，这得到了线性（即 Lippert-Mataga 和 Mac-Rae 极性函数）和多线性（即 Kamlet-Taft 和 Catalan 参数）分析的支持。此外，溶剂极化率（d）和溶剂偶极矩（C）是导致吸收和发射光谱红移的主要因素。电荷转移描述符以及极性图与广义 Mulliken-Hush（GMH）参数有很好的关系。使用溶剂化变色和计算方法研究了 7、8 和 9 的 NLO 性质。使用 DFT 与 B3LYP、BHHLYP 和 CAM-B3LYP 函数，确定了静态第一超极化率（β）和相关微观参数（μ、α、α、β、γ）。观察到含氮 phenanthroline 基化合物 9 的三阶 NLO 性质比化合物 7 和 8 高几个数量级，证明了设计方法的合理性。
