Synthesis, photophysical, linear, and non-linear optical properties of 4-methoxyphenyl dicyanovinylene dyes: DFT and TD-DFT studies

IF 4.3 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Pub Date : 2024-11-27 DOI:10.1016/j.saa.2024.125484

Mayuri S. Bagal, Aishwarya Zambare, Suryapratap Sharma, Nagaiyan Sekar

{"title":"Synthesis, photophysical, linear, and non-linear optical properties of 4-methoxyphenyl dicyanovinylene dyes: DFT and TD-DFT studies","authors":"Mayuri S. Bagal, Aishwarya Zambare, Suryapratap Sharma, Nagaiyan Sekar","doi":"10.1016/j.saa.2024.125484","DOIUrl":null,"url":null,"abstract":"<div><div>Dyes were synthesized via Knoevenagel condensation using various aldehydes of julolidine, n-hexylcarbazole, n-hexylphenothiazine, triphenylamine, and 7-N, N-diethylaminocoumarin named as MB1, MB2, MB3, MB4, and MB5. The dyes were characterized using FT-IR, 1H NMR, 13C NMR, and HRMS, which provided detailed structural information. Significant absorption, emission, and Stokes shift properties were observed through spectroscopic analysis. Notably, MB2, MB3, and MB4 exhibited solid-state and aggregation-induced emission (AIE) properties. MB1, MB3, and MB4 showed high viscosity sensitivity in polar solvents. Dyes containing nitrogen donors (MB1, MB2, and MB3) demonstrated acidochromism, responding to trifluoroacetic acid, while MB4 and MB5 remained neutral. Solvatochromic analysis indicated enhanced hyperpolarizabilities (<math><msub><mrow><mi>α</mi></mrow><mrow><mrow><mi>C</mi></mrow><mrow><mi>T</mi></mrow></mrow></msub></math>, <math><msub><mrow><mi>β</mi></mrow><mrow><mrow><mi>C</mi></mrow><mrow><mi>T</mi></mrow></mrow></msub></math> and <math><msub><mrow><mi>γ</mi></mrow><mrow><mrow><mi>C</mi></mrow><mrow><mi>T</mi></mrow></mrow></msub></math>) in polar solvents, with MB1 exhibiting the highest linear and second-order hyperpolarizability, making it ideal for non-linear optical (NLO) applications. MB5 also showed a notable solvent polarity response. Computational studies using B3LYP and CAM-B3LYP functionals confirmed increased hyperpolarizabilities in polar environments. All dyes displayed solvatochromism and promising NLO properties, with MB3 and MB5 showing lower band gaps and higher dipole moments in polar solvents, indicating their potential for photonics, bioimaging, and sensors.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"329 ","pages":"Article 125484"},"PeriodicalIF":4.3000,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1386142524016500","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"SPECTROSCOPY","Score":null,"Total":0}

引用次数: 0

Abstract

Dyes were synthesized via Knoevenagel condensation using various aldehydes of julolidine, n-hexylcarbazole, n-hexylphenothiazine, triphenylamine, and 7-N, N-diethylaminocoumarin named as MB1, MB2, MB3, MB4, and MB5. The dyes were characterized using FT-IR, ¹H NMR, ¹³C NMR, and HRMS, which provided detailed structural information. Significant absorption, emission, and Stokes shift properties were observed through spectroscopic analysis. Notably, MB2, MB3, and MB4 exhibited solid-state and aggregation-induced emission (AIE) properties. MB1, MB3, and MB4 showed high viscosity sensitivity in polar solvents. Dyes containing nitrogen donors (MB1, MB2, and MB3) demonstrated acidochromism, responding to trifluoroacetic acid, while MB4 and MB5 remained neutral. Solvatochromic analysis indicated enhanced hyperpolarizabilities (

α_{C T}

β_{C T}

and

γ_{C T}

) in polar solvents, with MB1 exhibiting the highest linear and second-order hyperpolarizability, making it ideal for non-linear optical (NLO) applications. MB5 also showed a notable solvent polarity response. Computational studies using B3LYP and CAM-B3LYP functionals confirmed increased hyperpolarizabilities in polar environments. All dyes displayed solvatochromism and promising NLO properties, with MB3 and MB5 showing lower band gaps and higher dipole moments in polar solvents, indicating their potential for photonics, bioimaging, and sensors.

Abstract Image

查看原文本刊更多论文

4-甲氧基苯基二氰乙烯染料的合成、光物理、线性和非线性光学性质：DFT和TD-DFT研究

以julolidine、n-己基咔唑、n-己基吩噻嗪、三苯胺和7-N， n-二乙基氨基香豆素为原料，分别以MB1、MB2、MB3、MB4和MB5为原料，通过Knoevenagel缩合法合成染料。利用FT-IR、1H NMR、13C NMR和HRMS对染料进行了表征，得到了详细的结构信息。通过光谱分析观察到显著的吸收、发射和斯托克斯位移特性。值得注意的是，MB2、MB3和MB4表现出固态和聚集诱导发射（AIE）性质。MB1、MB3和MB4在极性溶剂中具有较高的黏度敏感性。含有氮供体（MB1、MB2和MB3）的染料表现出酸致变色，对三氟乙酸有反应，而MB4和MB5保持中性。溶剂致变色分析表明，在极性溶剂中，MB1的超极化性（αCT、βCT和γCT）增强，其中MB1表现出最高的线性和二阶超极化性，使其成为非线性光学（NLO）应用的理想材料。MB5也表现出明显的溶剂极性响应。使用B3LYP和CAM-B3LYP泛函的计算研究证实，在极性环境中超极化率增加。所有的染料都表现出溶剂变色和良好的NLO性能，其中MB3和MB5在极性溶剂中表现出更小的带隙和更高的偶极矩，表明它们在光电子、生物成像和传感器方面的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 物理-光谱学

CiteScore

8.40

自引率

11.40%

发文量

1364

审稿时长

40 days

期刊介绍： Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (SAA) is an interdisciplinary journal which spans from basic to applied aspects of optical spectroscopy in chemistry, medicine, biology, and materials science. The journal publishes original scientific papers that feature high-quality spectroscopic data and analysis. From the broad range of optical spectroscopies, the emphasis is on electronic, vibrational or rotational spectra of molecules, rather than on spectroscopy based on magnetic moments. Criteria for publication in SAA are novelty, uniqueness, and outstanding quality. Routine applications of spectroscopic techniques and computational methods are not appropriate. Topics of particular interest of Spectrochimica Acta Part A include, but are not limited to: Spectroscopy and dynamics of bioanalytical, biomedical, environmental, and atmospheric sciences, Novel experimental techniques or instrumentation for molecular spectroscopy, Novel theoretical and computational methods, Novel applications in photochemistry and photobiology, Novel interpretational approaches as well as advances in data analysis based on electronic or vibrational spectroscopy.