Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines.,ChemPhysChem

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Combined Spectroscopic and TD-DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino- versus Nitro-Substituted 2,4-Diphenylquinolines.
ChemPhysChem ( IF 2.3 ) Pub Date : 2020-07-30 , DOI: 10.1002/cphc.202000452
Giovanny Carvalho Dos Santos _{1,

2} , Juan Carlos Roldao ₂ , Junqing Shi _{2,

3} , Begoña Milián-Medina ₄ , Luiz Carlos da Silva-Filho ₁ , Johannes Gierschner ₂

Affiliation

A combined spectroscopic and TD‐DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino‐ vs. nitro‐substituted 2,4‐diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset‐corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low‐lying n‐π* and ππ* transitions, which is decisive for the non‐/emissive nature of the different compounds. In all, this might provide a valuable tool for computer‐aided design of related classes of compounds.

中文翻译：

结合光谱和TD-DFT分析来阐明有机染料中的取代基和酸致变色效应：氨基和硝基取代的2,4-二苯基喹啉的案例研究。

结合光谱和TD-DFT案例研究进行了研究，以确定一种可靠的方法来计算各种氨基与硝基取代的2,4-二苯基喹啉在中性和连续酸性下变化很大的复杂的近UV / Vis吸收光谱条件。为此，测试了不同的DFT功能以优化几何形状，并测试了TD部分，以快速筛选方法计算中性和不同质子化的物种，即 e。在隐式溶剂中使用单点计算。迄今仅适用于聚合物的经偏移校正的M06HF被确定为以合理的方式再现所有不同取代模式和所有不同质子化物质在不同pH值下吸收光谱的合适方法；此外，该方法可以正确预测低位n-π*和ππ*跃迁的能量顺序，这对于不同化合物的非/发射性质具有决定性作用。总之，这可能为相关类别化合物的计算机辅助设计提供了一个有价值的工具。

更新日期：2020-07-30

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