Styryl-based new organic chromophores bearing free amino and azomethine groups: synthesis, photophysical, NLO, and thermal properties.

Anka Utama Putra,Deniz Çakmaz,Nurgül Seferoğlu,Alberto Barsella,Zeynel Seferoğlu

doi:10.3762/bjoc.16.189

Anka Utama Putra, Deniz Çakmaz + Show 3 more

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https://doi.org/10.3762/bjoc.16.189

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Abstract

Herein we report the synthesis and characterization of a new series of styryl-based push-pull dyes containing a free amino group and their Schiff base derivatives. The dyes include the dicyanomethylene group as an acceptor and different para-substituted alkylamines as donors. Morever as a proton-sensitive group a pyridin-2-yl substituent was attached to the para-position of the phenyl moiety in both series of compounds. The photophysical properties of the dyes were examined in various solvents with different polarities and showed absorption in the visible region and green-red emission with low quantum yields. The absorption and the emission maxima were shifted bathocromically by increasing the solvent’s polarity. However, there was no correlation with the polarity parameters of the solvents. The pH-sensitive properties of all prepared Schiff bases were examined against TBAOH in DMSO, via deprotonation of the OH group in the salicylidene moiety and their reverse protonation was also investigated using TFA. The Schiff bases exhibited a bathochromic shift upon the addition of TBAOH to their solutions in DMSO. Therefore, they showed potential to be utilized as colorimetric and luminescence pH sensors. The second-order nonlinear optical (NLO) responses of the dyes were measured by the electric field-induced second harmonic (EFISH) generation method. The highest μβ values were obtained for the dyes bearing the julolidine donor as 1430 × 10−48 esu (for free amino derivative) and 1950 × 10−48 esu (for Schiff base derivative), respectively. The structural and electronic properties of the dyes as well as their NLO properties were further studied using DFT calculations. The thermal stabilities of all dyes were evaluated by thermogravimetric analysis (TGA). The TGA data showed that all dyes were thermally stable up to 250 °C.

Highlights

Push-pull organic molecules are a class of organic dyes comprising of electron-donating and accepting groups in a donor–π–acceptor (D–π–A) system
As depicted in Scheme 1, dye 2 was obtained in good yield by reacting malononitrile and 4-aminoacetophenone according to our previous published procedure [31,32]
The styryl-based organic chromophores 3–7 having a free amino and strong donor-acceptor groups and a pyridin-2-yl moiety were synthesized by the base-catalyzed condensation of 2 with different aldehyde derivatives in ethanol, as depicted in Scheme 1

Summary

Introduction

Push-pull organic molecules are a class of organic dyes comprising of electron-donating and accepting groups in a donor–π–acceptor (D–π–A) system. The flexibility to change electron-donor and acceptor groups in the molecules allows to tune intramolecular charge transfer (ICT) intensity and it can increase NLO properties [11,12,13,14]. Some ions such as proton (H+) and hydroxide (OH−), in aqueous environments, play significant roles in industrial, biological, and environmental processes [15,16,17]. PH-sensitive dyes play a critical role in various sensor applications for easy determination of such ions These dyes show different spectral properties upon protonation/deprotonation processes [23,24,25]. Some fluorescent dyes demonstrate remarkable ICT characteristics, and could serve as NLO dyes [11,12,13,14]

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