Effect of multi-donor and extended π-conjugation in ferrocene appended indanedione chromophores for aggregation induced emission enhancement (AIEE) and nonlinear optics†

IF 4.1 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2024-08-29 DOI:10.1016/j.dyepig.2024.112422

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Abstract

A new (D-D’π-A) type ferrocene and methoxyphenyl (D-D′) conjugated indanedione (A) based linear and π-extended multi-donor-π-acceptor chromophores 1–4 were synthesized and characterized. The chromophores 2–4 were further investigated by single-crystal analysis through X-ray diffraction, revealing centrosymmetric space groups with non-covalent interactions (inter, intramolecular hydrogen bonding, and C–H…π interactions) and these molecular packing interactions favor SHG efficiencies. Electrochemical studies show the one-electron charge transfer (Fe²⁺⇌Fe³⁺) and observed greater redox potential of chromophore 4 than the parent ferrocene due to the substitution effect. The solvatochromic studies in emission spectra resulted in redshift (56–109 nm) for the chromophores 1–4 by increasing the solvent polarities, which indicates higher excited state stabilization relative to the ground state, results effective intramolecular charge transfer process within the chromophores. The occurrence of ferrocene moieties lowers the fluorescence intensities of the chromophores 1–4, which was overcome through aggregation induced emission enhancement (AIEE) studies at 60 % (THF/H₂O). The AIEE state also shows 23 times higher quantum yield than the THF solution for chromophore 4. In addition, a thin film using polymethyl methacrylate as a binder shows a significant blue shift with higher emission intensity than those obtained in the solution due to the intermolecular interactions and enhancement of viscosity. The SHG efficiency studied using the Kurtz and Perry powder technique results in a higher value for chromophore 4 (2 times higher than the reference KDP) attribute to the multi donors, acceptor, and extended π conjugation reducing the anti-parallel alignment in the solid state. The computational calculations were done to validate the experimental results using B3LYP/6-31+G** level of theory.

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二茂铁添加茚二酮发色团中的多供体和扩展π共轭对聚集诱导发射增强（AIEE）和非线性光学的影响†

合成并表征了一种新的（D-D'π-A）型二茂铁和甲氧基苯基（D-D′）共轭茚二酮（A）基线性和π-扩展多供体-π-受体发色团 1-4。通过 X 射线衍射对单晶分析对发色团 2-4 进行了进一步研究，发现其中心对称空间基团具有非共价相互作用（分子间、分子内氢键和 C-H...π 相互作用），这些分子堆积相互作用有利于 SHG 效率的提高。电化学研究显示了单电子电荷转移（Fe2+⇌Fe3+），并观察到由于取代效应，发色团 4 的氧化还原电位高于母体二茂铁。在发射光谱中进行的溶解变色研究发现，通过增加溶剂极性，发色团 1-4 的发射光谱会发生红移（56-109 nm），这表明相对于基态，激发态的稳定性更高，从而在发色团内部实现了有效的分子内电荷转移过程。二茂铁分子的存在降低了发色团 1-4 的荧光强度，在 60% （THF/H2O）的条件下进行的聚集诱导发射增强（AIEE）研究克服了这一问题。在 AIEE 状态下，发色团 4 的量子产率也比 THF 溶液高出 23 倍。此外，使用聚甲基丙烯酸甲酯作为粘合剂的薄膜显示出显著的蓝移，由于分子间的相互作用和粘度的增强，其发射强度比溶液中获得的更高。利用库尔兹和佩里粉末技术对 SHG 效率进行了研究，结果发现发色团 4 的 SHG 效率值更高（比参考 KDP 高 2 倍），这归因于多供体、受体和扩展的 π 共轭减少了固态中的反平行排列。为了验证实验结果，我们使用 B3LYP/6-31+G** 理论水平进行了计算。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.