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Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations
Accepted Manuscript Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations Çiğdem Karabacak Atay, Merve Gökalp, Sevgi Özdemir Kart, Tahir Tilki PII:
S0022-2860(17)30396-4
DOI:
10.1016/j.molstruc.2017.03.107
Reference:
MOLSTR 23603
To appear in:
Journal of Molecular Structure
Received Date: 22 January 2017 Revised Date:
21 March 2017
Accepted Date: 29 March 2017
Please cite this article as: E. Karabacak Atay, M. Gökalp, S.E. Kart, T. Tilki, Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.03.107. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Graphical Abstract: The synthetic scheme for the preparation of compound A-D.
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Mono Azo Dyes Derived From 5-Nitroanthranilic Acid: Synthesis, Absorption
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Properties and DFT Calculations
3 Çiğdem KARABACAK ATAY1, Merve GÖKALP2, Sevgi Özdemir KART3, Tahir TİLKİ2
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[email protected]
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Mehmet Akif Ersoy University, Education Faculty, Elementary Education Department, 15030, Burdur, Turkey 2
Süleyman Demirel University, Faculty of Science & Arts, Chemistry Department, 32260, Isparta, Turkey 3
PamukkaleUniversity, Faculty of Science & Arts, Physics Department, 20070, Denizli, Turkey
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Four new azo dyes: 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A), 2-[(3-hydroxy-5-
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methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic
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nitrobenzoic acid (C) and 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D) which have
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the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups are synthesized in this work.
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The structures and spectroscopic properties of these new azo dyes are characterized by using spectroscopic
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methods such as FT-IR, 1H-NMR, 13C-NMR and UV–vis. Their solvatochromic properties in chloroform, acetic
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acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO) are studied. Moreover, molecular
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structures and some spectroscopic properties of azo dyes are investigated by utilizing the quantum computational
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chemistry method based on Density Functional Theory (DFT) employing B3LYP hybrid functional level with 6-
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31G(d) basis set. It is seen that experimental and theoretical results are compatible with each other.
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(B),
2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-
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Keywords: Anthranilic acid, Heterocyclic dye, Spectroscopic property, Density Functional Theory.
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1. Introduction
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Azo compounds are, a class of chemical compounds, currently receiving attention in scientific and technological
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research [1-4]. These chemical materials are colored compounds which are yellow, red, orange, blue or even
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green, depending on the structure of the molecule. Azo compounds are important materials which are used in the
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different areas [5-13]. Especially, computational and structural researches on azo dyes have been interested in
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the fields of dye chemistry as well as in dye industry in recent years, because these studies have been carried out
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to reveal the structure-performance relationship of dyes [14-18]. In our previous works [19,20], we have
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investigated the structural and spectral properties of a series of disazo dyes and performed computational studies
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based on Density Functional Theory (DFT). Recently, Sener et. al [21] have synthesized disazo dye containing
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pyrazole skeleton and characterized its structure by using FT-IR, 1H NMR and
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coumarin based disazo dyes have been synthesized and their spectroscopic properties have been clarified by
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experimental as well as theoretical investigations carried out by Yıldırım et. al [22].
C NMR. A series of novel
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In this study, our main aim is to investigate the structure-performance relationship of some mono azo dyes which
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are synthesized by coupling cyclizated active methylene compounds such as malondinitrile, ethylacetoacetate,
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acetylacetone and 3-aminocrotononitrile with diazonium salts derived from anthranilic acid by performing
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experimental studies and computational calculations. FT-IR and H-NMR spectra of four new azo dyes are
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measured in order to obtain the chemical structural properties. The molecular structure, vibrational and NMR
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spectra of the azo dyes synthesized in this work are calculated by using DFT method with the basis set of 6-
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31G(d). Crystal structures such as bond length, bond angle and dihedral angles of azo dyes compounds
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considered in this work are identified by quantum computational method based on DFT.
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2.1. Synthesis of 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A)
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2 mmol of 5-nitroanthranilic acid is dissolved in hydrochloric acid (in 5 ml water). Then, the solution is cooled
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to 0-5oC with stirring. Sodium nitrite (2 mmol) in water (5 ml) is gradually added to this solution over 15 min
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period at 0-5oC while stirring. The reaction mixture is stirred for 2h at this temperature. The resulting diazonium
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salt solution is then added dropwise to a well-cooled and stirred solution of malononitrile (2 mmol) in sodium
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acetate (2 g) dissolves in 20 mL water. The pH is maintained at 4-6 through the coupling process by adding
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sodium acetate. Stirring is continued for 4h at 0-5oC. The precipitated products diluted with cold water (50 mL),
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filtered off, washed with water several times, and dried. The obtained product is recrystallized from DMF-H2O
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mixture. Hydrazine hydrate (0.5 mL) is added to a solution of this obtained product (3 mmol) in 20 ml ethanol.
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The reaction mixture is heated under reflux for 4-6h and then cooled at room temperature. Upon water being
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added, precipitate product is filtered, washed with water several times, and dried. The obtained product 2-[(3,5-
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diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A) is recrystallized from DMF-H2O mixture.
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2.2. Synthesis of 2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B)
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2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B) is synthesized by following
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procedure of 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A). However, instead of
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malononitrile, ethylacetoacetate is used as an active methylene compound in the synthesis of compound (B).
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2.3. Synthesis of 2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (C)
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The procedure followed to syhtesize the Compound A is used for the synthesis of 2-[(3,5-dimethyl-1H-pyrazol-
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4-yl)diazenyl]-5-nitrobenzoic acid (C), except for active methylene compound. Acetylacetone is used instead of
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malononitrile.
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2.4. Synthesis of 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D)
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The synthesize procedure of title Compound D is the same as that of Compound A. Only different point from the
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synthesis of Compound A is that 3-aminocrotononitrile is used as an active methylene compound in the synthesis
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of compound D.
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The synthesis schemes for the preparation of compounds A-D are given in Figure 1 as mentioned above.
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2.5. Experimental equipments
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IR spectra for new azo dyes are performed by Schimadzu IR Prestige-21 Fourier Transform-infrared (FT-IR)
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spectrophotometer. Nuclear magnetic resonance spectra of all synthesized compounds are assigned with Bruker
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Avance 125 MHz. All of the wavenumbers for new azo dyes synthesized in this work are measured with
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Schimadzu UV-1601 double beam spectrophotometer at the various concentrations. Melting points were
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recorded on an Smart SMP30 Stuart melting point apparatus.
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3. Computational method
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ACCEPTED MANUSCRIPT The DFT based on B3LYP hybrid functional with 6-31G(d) basis set is used to calculate the structural and
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vibrational properties of four new azo dyes which are synthesized in this work [23,24]. Theoretical calculations
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for new azo dyes are performed by utilizing the GAUSSIAN 09W package based on quantum chemical
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calculation techniques [25]. The DFT method is a powerful tool to satisfy performance in terms of the desired
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sensitivity, computation time and power [26]. The DFT calculations based on B3LYP level are much more
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sensitive results in predicting structural and electronic characteristics than Hartree-Fock (HF) methods [27]. The
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optimal structures of the new azo dyes are obtained by using the B3LYP/6-31G(d) level. The optimized
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geometric structures of the azo dyes compounds are given in Figure 2. Vibrational modes of the molecules
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considered in this work are calculated with the help of vibration spectrum analysis by following the optimized
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structure of azo dyes. The DFT method tends to overestimate the vibrational modes; therefore scaling factor
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(0.9613) has to be used to overcome the insufficiencies of the theoretical approximations used in the
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calculations. Therefore, the results are attained to agreement with the corresponding experimental data [28]. All
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of the wavenumbers for new azo dyes synthesized in this work are found to be positive, providing that a true
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minimum on the potential surface. The vibrational data obtained from theoretical studies are assigned with the
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GAUSSVIEW 5.0.8 and the VEDA4 programs [29,30]. The 1H-NMR chemical shift data for the new azo dyes
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are predicted by using the same level method considered in this work via the Gauge-Including Atomic Orbital
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(GIAO) method [31]. The 1H-NMR chemical shift calculations are analyzed by considering Tetramethylsilane
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(TMS) as a reference. UV-vis spectrum analyses of azo dyes considered in this work are studied by using Time
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Dependent Density Functional Theory (TD-DFT) employing B3LYP level with the basis set of 6-31G(d) in the
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different solvents.
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4. Results and discussion
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Physical properties of Compounds A-D were listed in Table 1. The determination of tautomerism is important,
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especially for theoretical studies, because of their different properties such as photo-physical, biological, thermal
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and technical. Compound B can exist in four possible tautomeric forms, namely, the azo-enol form, hydrazo-keto
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form, the azo-keto form and the hydrazo-enol form. The deprotonation of tautomeric forms of Compound B lead
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to common anions. Also, Compound A, C and D can exist in two possible tautomeric forms, namely, the azo
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form and the hydrazo form. Tautomeric forms of Compounds A-D are shown in Figure 3.
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shown in the figure indicate that as the transmittance is low, absorption is high. When any peaks are not
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observed in the figure, photons are not observed. Therefore, it can be said that Compound A has not a specific
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vibrations at the wavenumber considered. The FT-IR spectra of Compounds A-D shows aromatic (Ar–H) band
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at 3420–3280 cm−1, aliphatic (Alip–H) band at 3040–2880 cm−1 and azo (N=N) band at 1580–1480 cm−1. FT-IR
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spectra of dyes are given in Figure S1 (Supplementary data, Appendix A). As corresponding B3LYP/6-
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31G(d) predictions, aromatic (Ar-H) band is recorded within the region of 3129–3095 cm−1. The FT-IR spectra
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of aliphatic (Alip–H) and azo (N=N) bands are calculated as values of 2943–2931 cm−1 and at those of 1485–
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1425 cm−1, respectively. 84 normal modes of the vibrations are observed for Compound A; 29 modes are
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stretching vibrations, 28 modes are bending vibrations and the rest, 27 modes, are torsional vibrational for
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Compound A. As for Compound B, 84 normal modes of the vibrations are obtained. 29 modes of these
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vibrations are stretching vibrations, 28 modes are bending vibrations and 27 modes are torsional vibrations. The
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Compound C has 90 normal modes of the vibrations; 31, 30 and 29 modes of these are stretching vibration,
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bending vibration and torsional vibrations, respectively. Finally, the normal modes of the vibrations of
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Compound D are made up of 30 modes of stretching vibrations, 29 modes of bending vibrations and 28 modes of
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torsional vibrations. The vibrational frequencies produced by DFT method within 6-31G(d) basis set are
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multiplied by a scale factor of 0.9613 to match experimental vibrational frequencies [28]. The values of
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vibrational frequencies calculated by B3LYP/6-31G(d) method are given in Table 2, along with experimental
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data. It is seen that theoretical data are in good agreement with experimental results except for a few
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wavenumbers.
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The vibrational frequencies of all synthesized compounds are assigned with GAUSSVIEW 5.0.8 and the
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VEDA4 programs. The linear regression of Compound A between theoretical and experimental frequencies is
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shown in Figure 5. Linear regression is carried out by using the linear equation of ݔܽ = ݕ+ ܾ , where ܽ and ܾ
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are fit constants. The correlation between the experimental and the calculated frequencies multiplied by scale
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factor of Compound A is linear as shown in Figure 5. The equality of = ݕ1.0037 ݔ− 3.2699 (ܴ = 0.9998) is
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obtained by using the method of DFT/B3LYP. It can be concluded that the frequency values obtained from the
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method of DFT/B3LYP is consistent with the experimental data, since the slope goes to unity as shown in
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Figure 5. The correlation value (ܴ) is found as 0.9998.
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illustrated in Figure 6. The measurement spectra of 1H-NMR for Compounds A, B and C are given in Figure S2
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(Supplementary data, Appendix A). 1H-NMR chemical shift spectra of compounds show broad peaks between
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7.42 and 6.30 ppm (NH2), and between 15.92 and 11.21 ppm (NH) of pyrazole. The other chemical shift δ values
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of 8.74–7.53 ppm (aromatic H), 2.17-2.00 ppm (CH3) for pyrazole and 16.58–15.80 ppm (OH) for carboxylic
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acid are recorded.
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128.09 and 115.81 ppm were observed and assigned to pyrazole carbons (C17, C14 and C13) and 157.14,
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141.35, 120.42, 113.55, 113.23 and 111.76 ppm were observed and defined to phenyl carbons (C4, C1, C3, C2,
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C6 and C5) of Compound D. Also, 167.13 ppm was identified to carbonyl carbon (C8) and 9.87 ppm was
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assigned to methyl carbon (C19). The measurement spectra of 13C-NMR for Compounds A, B and C are given in
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Figure S3 (Supplementary data, Appendix A). The theoretical 1H and 13C NMR data are computed by using
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B3LYP/6-31G(d) in the gas phase. The 1H-NMR values calculated for Compounds A-D in the solvent of DMSO
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and corresponding experimental data are given in Table 3. As we consider the 1H-NMR values calculated by
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B3LYP/6-31G(d), the compounds show broad peaks between 4.79 and 3.08 ppm (NH2), and between 8.48 and
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6.51 ppm (NH) for pyrazole. The other chemical shift δ values of 8.12–7.19 ppm (aromatic H), 2.47-1.89 ppm
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(CH3) for pyrazole and 5.59–5.74 ppm (OH) for carboxylic acid are obtained. When compare the theoretical
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results and experimental data of 1H-NMR, except for X-H (-OH, NH), aromatic and aliphatic protons are in good
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agreement with each other. It can be clearly seen that -OH and -NH protons resonate at the different regions in
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our theoretical studies. This indicates that the tautomerization occurs in these compounds. Experimental and
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theoretical chemical shifts give ones useful information about chemical structure of compounds. Comparison of
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general, the chemical shifts values of the aromatic carbons appear in the range of 100–160 ppm.
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UV-spectra analyses of compounds are investigated experimentally for five different solvents of DMF,
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methanol, acetic acid, chloroform and DMSO. Compounds A-D gave a single absorbance without shoulder in all
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solvents. Compounds A, B and C were the largest in DMSO when compared with other four solvents. Also,
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λmax values of Compounds A, B and C in DMF were larger than λmax in acetic acid, chloroform and methanol.
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Compound D was the largest in DMF. It was also observed that λmax values of Compounds A-D in methanol,
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acetic acid, DMSO and DMF were shifted bathochromically according to the λmax in chloroform. These results
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suggest that Compound B is present as an anionic form in DMSO and as a tautomeric form in DMF and as a
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different tautomeric form in chloroform, methanol and acetic acid. TD-DFT is also used to compute the UV-vis
H-NMR spectra of azo dyes synthesized in this work are measured and as an example, that of Compound D is
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C NMR resonances at 151.31,
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C-NMR spectrum for Compound D is given in Figure 7.
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C-NMR experimental values with those calculated from B3LYP/6-31G(d) method are listed in Table 4. In
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depends on the nature of the media. Therefore, absorption spectra of title compound in solvents with different
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polarities are systematically investigated. UV spectrum analyses of compounds are listed in Table 5. Absorption
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spectrum of Compound A is shown in Figure 8. Due to solubility problems, absorption spectra are determined at
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various concentrations (10−6–10−8 M) between 300 and 700 nm. The UV–vis spectra shows that bathochromic
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shifts of λmax values of compounds observed in DMSO and DMF are greater than those in the other solvents. On
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the other hand, the calculated λmax values of compounds do not show significant change in all solvents.
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Carbon-carbon and carbon-hydrogen bonds are the building blocks for organic compounds. In heteroatom-
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containing compounds, as well as these bonds, the bonds of heteroatoms with each other and with hydrogen are
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important. For this reason, the measurements of bond lengths and bond angles are indispensable for the
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theoretical studies of organic compounds. The optimized structure parameters values in the ground state for
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compound A are seen in Table 6. All the computed structural parameters for Compounds B, C and D are
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provided in the Table S1, S2 and S3 as a Supplementary material to compare with each other. Carbon-carbon
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bond length values for Compound A are computed in the between 1.3873 and 1.5009 Å by using DFT/B3LYP
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level with 6-31G(d). Nitrogen-nitrogen bond length value is found as 1.2837 Å for Compound A. Nitrogen-
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hydrogen bond length values for Compound A are in the between 1.0080 and 1.0164 Å. Oxygen-carbon-oxygen
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bond angle value of Compound A is 122.5176o while oxygen-carbon-oxygen-hydrogen dihedral angle value is
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computed as -3.5611o.
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5. Conclusion
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Four new azo dyes having the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups have
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been synthesized in this work. The structures and spectroscopic properties of azo dyes have been characterized
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by using spectroscopic methods such as FT-IR, 1H-NMR, 13C-NMR and UV–vis. Additionally, solvatochromic
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properties in chloroform, acetic acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO)
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have been studied. DFT method employing B3LYP level with 6-31G(d) basis set is also used to verify the
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molecular structure and spectroscopic properties of azo dyes synthesized in this study. The chemical shift
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calculations for 1H NMR and
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(GIAO) method. The positions of hydrogen and carbon atoms of molecules considered in this work are
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determined by means of computed 1H and 13C NMR chemical shifts. UV-vis spectrum analyses of all azo dyes
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C-NMR of azo dyes are carried out by using Gauge-Invariant Atomic Orbital
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by using both experimental and theoretical research on four new azo dyes considered in this work are performed
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for the first time. The theoretical data are compared with experimental values. The theoretical results and
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experimental data are in good agreement with each other. The experimental and theoretical comparisons are very
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useful to make correct assignment and to understand the basic vibrational, NMR spectra and molecular structure.
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This study also shows that DFT theory with B3LYP/6-31G(d) level calculations are powerful approach to
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investigate the structural and vibrational properties of azo dyes compounds. This study may be extended to study
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electronic properties of azo dyes by using DFT method in the future.
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Appendix A. Supplementary material
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Supplementary data associated with this article can be found, in the online version, at http://
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[21] N. Sener, A. Bayrakdar, H.H. Kart, I. Sener, A combined experimental and DFT investigation of disazo dye having pyrazole skeleton, J. Mol. Struc. 1129 (2017) 222-230.
RI PT
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[22] F. Yıldırım, A. Demirçalı, F. Karcı, A. Bayrakdar, P. Tunay Taşlı, H.H. Kart, New coumarin-based disperse
279
disazo dyes: Synthesis, spectroscopic properties and theoretical calculations, J. Mol. Liq. 223 (2016) 557–
280
565.
282 283 284
[23] C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B. 37 (1988) 785-789.
M AN U
281
SC
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[24] A. D. Becke, Density‐functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98 (1993) 5648–5652.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V.
286
Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J.
287
Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
288
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M.
289
Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari,
290
A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N.J. Millam, M. Klene, J.E. Knox, J.B.
291
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi,
292
C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.
293
Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox,
294
Gaussian 09, Gaussian, Inc., Wallingford CT, 2009.
296
EP
AC C
295
TE D
285
[26] M.A. Palafox, N. Iza, M. Gil, The hydration effect on the uracil frequencies: an experimental and quantum chemical study, J. Mol. Struct. (Theochem.) 585 (2002) 69-92.
297
[27] M. Karakus, S. Solak, T. Hökelek, H. Dal, A. Bayrakdar, S. Özdemir Kart, M. Karabacak, H. H. Kart,
298
Synthesis, crystal structure and ab initio/DFT calculations of a derivative of dithiophosphonates,
299
Spectrochim. Acta A. 122 (2014) 582–590.
10
ACCEPTED MANUSCRIPT 300 301
[28] J.P. Merrick, D. Moran, L. Radom, An Evaluation of Harmonic Vibrational Frequency Scale Factors, J. Phys. Chem. A. 111 (2007) 11683-1170. [29] R. D. Dennington, T. A. Keith, J. M. Millam, GaussView 5.0.8, Gaussian Inc., 2008.
303
[30] M. H. Jamroz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004.
304
[31] R. Ditchfiled, Molecular Orbital Theory of Magnetic Shielding and Magnetic Susceptibility, J. Chem. Phys.
305
56 (1972) 5688–5691.
RI PT
302
306 307
SC
308 309 310
M AN U
311 312 313 314
318 319 320 321 322 323 324
EP
317
AC C
316
TE D
315
325 326 327 328 329
11
ACCEPTED MANUSCRIPT Figure Captions
331
Figure 1. The synthetic scheme for the preparation of Compounds A-D.
332
Figure 2. The calculated optimized structures of Compounds A-D at the level of DFT/B3LYP with the basis of
333
6-31G(d).
334
Figure 3. Tautomeric forms of Compounds A-D.
335
Figure 4. Transmittance versus wavenumber of Compound A computed from DFT/B3LYP method with 6-
336
31G(d) basis set.
337
Figure 5. The linear regression between the experimental and theoretical frequencies of Compound A.
338
Figure 6. 1H-NMR spectrum for Compound D.
339
Figure 7. 13C-NMR spectrum for Compound D.
340
Figure 8. The measurement absorption spectrum of Compound A.
342 343 344
349 350 351 352 353 354
EP
348
AC C
347
TE D
345 346
SC
M AN U
341
RI PT
330
355 356 357 358 359
12
ACCEPTED MANUSCRIPT 360
Figure 1.
SC
RI PT
361
M AN U
362 363 364 365 366
370 371 372 373 374 375 376
EP
369
AC C
368
TE D
367
377 378 379 380 381 13
ACCEPTED MANUSCRIPT 382
Figure 2.
RI PT
Compound A
M AN U
SC
Compound B
AC C
EP
TE D
Compound C
Compound D
383
14
ACCEPTED MANUSCRIPT
384
Figure 3.
Compound A
M AN U
SC
RI PT
Compound C
Compound D
AC C
EP
TE D
Compound B
15
ACCEPTED MANUSCRIPT Figure 4.
SC
RI PT
385
386
M AN U
387 388 389 390
394 395 396 397 398 399 400 401
EP
393
AC C
392
TE D
391
402 403 404 405 406 16
ACCEPTED MANUSCRIPT 407
Figure 5.
SC
RI PT
Experimental (cm-1)
408
M AN U
409 410
Calculated (cm-1)
411 412
416 417 418 419 420 421 422
EP
415
AC C
414
TE D
413
423 424 425 426 427
17
ACCEPTED MANUSCRIPT 428
Figure 6.
432 433 434 435 436
EP
431
AC C
430
TE D
M AN U
SC
RI PT
429
437 438 439 440 441 18
ACCEPTED MANUSCRIPT 442
Figure 7.
M AN U
SC
RI PT
443
447 448 449 450 451 452 453
EP
446
AC C
445
TE D
444
454 455 456 457 458
19
ACCEPTED MANUSCRIPT Figure 8.
M AN U
SC
RI PT
459
460 461
465 466 467 468 469 470 471
EP
464
AC C
463
TE D
462
472 473 474 475 476
20
ACCEPTED MANUSCRIPT Table Captions
478
Table 1. Physical properties of Compounds A-D.
479
Table 2. Comparison of FT-IR experimental values with those obtained from B3LYP/6-31G(d) method.
480
Table 3. Comparison of 1H-NMR experimental values with those calculated from DFT method.
481
Table 4. Comparison of 13C-NMR experimental values with those calculated from B3LYP/6-31G(d) method.
482
Table 5. The effect of solvent on λmax (nm) obtained by experimentally and theoretically for Compounds A-D.
483
Table 6. The structure parameters optimized in the ground state for Compound A; Bond length (Å), bond angle
484
(o) and dihedral angle (o).
RI PT
477
SC
485 486 487
M AN U
488 489 490 491
495 496 497 498 499 500 501
EP
494
AC C
493
TE D
492
502 503 504 505 506
21
ACCEPTED MANUSCRIPT 507
Table 1. Compound
Molecular formula
m.p. (oC) (colour)
(m. wt)
(%)
C10H9N7O4 (291.22)
275.7 (dark brown)
67
B
C11H9N5O5 (291.22)
285.4 (yellow)
86
C
C12H11N5O4 (289.25)
189.4 (dark yellow)
74
D
C11H10N6O4 (290.23)
218.6 (brown)
509
511
M AN U
512 513 514 515 516
522 523 524 525 526
EP
521
AC C
520
TE D
517
519
78
SC
510
RI PT
A
508
518
Yield
527 528 529 530 531 22
ACCEPTED MANUSCRIPT 532
Table 2. Vibrational frequencies (cm-1) Compound
(A)
Experiment
DFT/B3LYP*
νAr-H
νAlip-H
νN=N
νAr-H
νAlip-H
νN=N
3420
--
1580
3095 (C3-H30)
-
1466
3128 (C2-H29) (B)
3320
2960
1540
3095 (C3-H30)
2933 (C18-H22H26H27)
1485
3098 (C3-H31)
2931 (C18-H22H26H27)
1468
3127 (C6-H29)
2943 (C19-H24H28H32)
3128 (C6-H28) 3129 (C2-H29) 3280
2880
1520
SC
(C)
RI PT
3122 (C6-H28)
3129 (C2-H30) (D)
3320
3040
1480
3098 (C3-H30)
M AN U
3122 (C6-H28) 3129 (C2-H29)
533
*basis set 6-31G(d), scale factor 0.9613 [28]
534 535
539 540 541 542 543
EP
538
AC C
537
TE D
536
2943 (C19-H24H27H31)
23
1425
ACCEPTED MANUSCRIPT
Table 3. 1
H-NMR (d, ppm, DMSO-d6)
(A)
Aro-H
Alip-H
X-H
Aro-H
7.94-8.46 (m. 3H)
-
6.30 (pyrazole NH2)
-
7.42 (pyrazole NH2)
7.19-7.98 (m. 3H)
16.50 (OH)
7.94-8.62 (m. 3H)
2.17 (s. 3H pyrazole CH3)
2.00 (s. 6H pyrazole CH3)
11.44 (pyrazole NH)
3.15-4.33 (pyrazole NH2)
1.89-2.39 (s. 3H pyrazole CH3)
6.51 (pyrazole NH) 5.67 (OH) 7.82 (pyrazole NH)
15.80 (OH)
5.66 (OH)
11.21 (pyrazole NH)
7.50-8.12 (m. 3H)
7.38 (pyrazole NH2)
7.37-8.03 (m. 3H)
TE D
2.01 (s. 3H pyrazole CH3)
-
8.46 (pyrazole OH)
1.90-2.47 (s. 3H pyrazole CH3)
8.48 (pyrazole NH)
1.91-2.11 (s. 3H pyrazole CH3)
5.59 (OH)
1.72-2.01 (s. 3H pyrazole CH3)
3.29-4.56 (pyrazole NH2) 7.28 (pyrazole NH)
16.58 (OH)
5.74 (OH)
EP
15.92 (pyrazole NH)
AC C
7.53-8.71 (m. 3H)
3.08-4.79 (pyrazole NH2)
13.29 (pyrazole OH)
16.50 (OH) (D)
7.28-8.11 (m. 3H)
M AN U
(C)
7.98-8.74 (m. 3H)
X-H
-
SC
11.31 (pyrazole NH)
(B)
Alip-H
RI PT
Compound
DFT/B3LYP
24
ACCEPTED MANUSCRIPT
Table 4. Experimental
Chemical shift values of 13C-NMR* (ppm)
13C-NMR (DMSO-d6)
Compound B
Compound C
Compound D
Compound A
Compound B
Compound C
Compound D
157.50 (C8)
153.51 (C8)
154.21 (C8)
158.00 (C8)
168.79 (C8)
166.56 (C8)
169.53 (C8)
167.13 (C8)
145.55 (C4)
143.94 (C4)
145.48 (C4)
145.69 (C4)
156.49 (C4)
158.48 (C4)
154.14 (C4)
157.14 (C4)
134.03 (C17)
140.44 (C14)
136.12 (C17)
136.59 (C17)
152.77 (C17)
149.19 (C14)
145.05 (C17)
151.31 (C17)
131.14 (C14)
133.24 (C17)
132.83 (C1)
131.62 (C1)
144.64 (C14)
147.14 (C17)
135.22 (C1)
141.35 (C1)
131.02 (C1)
132.85 (C1)
127.94 (C14)
128.26 (C14)
143.58 (C1)
141.68 (C1)
129.28 (C14)
128.09 (C14)
113.54 (C3)
115.93 (C13)
125.56 (C13)
114.74 (C3)
130.20 (C3)
131.97 (C13)
127.89 (C13)
120.42 (C3)
113.53 (C2)
115.40 (C3)
116.52 (C3)
113.93 (C13)
126.17 (C2)
127.14 (C3)
122.79 (C3)
115.81 (C13)
112.35 (C6)
115.01 (C6)
114.46 (C6)
113.49 (C2)
125.77 (C6)
126.78 (C6)
115.98 (C6)
113.55 (C2)
110.83 (C5)
114.12 (C2)
113.70 (C2)
112.09 (C6)
120.59 (C5)
114.54 (C2)
114.04 (C2)
113.23 (C6)
106.81 (C13)
111.44 (C5)
110.72 (C5)
110.78 (C5)
115.94 (C13)
113.55 (C5)
95.35 (C5)
111.76 (C5)
1.55 (C18)
9.64 (C19)
11.78 (C18)
10.22 (C19)
9.87 (C19)
M AN U
TE D
AC C
*Reference: TMS B3LYP/6-311+G(2d,p) GIAO.
8.89 (C19)
EP
1.60 (C18)
SC
Compound A
RI PT
DFT/B3LYP
25
10.22 (C18)
ACCEPTED MANUSCRIPT Table 5. Experiment Compound
DMSO
DMF
B3LYP/B3LYP/6-31G(d)
Methanol
Acetic
Chloroform
DMSO
DMF
Methanol
Acid
Acetic
Chloroform
Acid
478
472
438
400
346
488
487
487
478
475
(B)
442
430
402
400
398
436
436
436
436
436
(C)
390
378
354
348
350
475
475
474
474
474
(D)
442
446
384
376
340
465
465
464
463
463
AC C
EP
TE D
M AN U
SC
RI PT
(A)
26
ACCEPTED MANUSCRIPT Table 6. DFT/ B3LYP/6-31G(d) 1.3952 1.3950 1.3873 1.4048 1.0851 1.4198 1.4042 1.3902 1.5009 1.3548 1.2156 1.2837 1.3414 1.4484 1.3205 1.0164 1.0102 1.0080 1.4038 0.9759 1.2324 1.2323 1.0105 1.0122
SC
RI PT
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 N18-H23 N18-H22 N16-H24 N15-N16 O9-H27 N7-O20 N7-O21 N19-H26 N19-H25
M AN U
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-23) R(18-22) R(16-24) R(15-16) R(9-27) R(7-20) R(7-21) R(19-26) R(19-25)
H22-N18-H23 N15-N16-H24 H25-N19-H26 N11-N12-C13 C4-N11-N12 C8-O9-H27 O9-C8-O10 O20-N7-O21
EP
AC C
A(22,18,23) A(15,16,24) A(25,19,26) A(11,12,13) A(4,11,12) A(8,9,27) A(9,8,10) A(20,7,21)
TE D
Bond Angles (º)
D(10,8,9,27) D(16,17,18,22) D(16,17,18,23) D(11,12,13,14)
115.4356 117.6179 117.9513 119.1514 111.2886 106.1096 122.5176 124.5213
Dihedral Angles (º) O10-C8-O9-H27 N16-C17-N18-H22 N16-C17-N18-H23 N11-N12-C13-C14
27
-3.5611 -26.1243 -170.7766 -3.9886
ACCEPTED MANUSCRIPT Appendix A Supplementary data for
Properties and DFT Calculations
RI PT
Mono Azo Dyes Derived From 5-Nitroanthranilic Acid: Synthesis, Absorption
1
Mehmet Akif Ersoy University, Education Faculty, Basic Education Department, 15030, Burdur, Turkey
Süleyman Demirel University, Faculty of Science & Arts, Chemistry Department, 32260, Isparta, Turkey PamukkaleUniversity, Faculty of Science & Arts, Physics Department, 20070, Denizli, Turkey
AC C
EP
TE D
3
M AN U
2
SC
Çiğdem KARABACAK ATAY1*, Merve GÖKALP2, Sevgi Ozdemir KART3, Tahir TİLKİ2
_____________________________________________ * Corresponding author, Mehmet Akif Ersoy University, Education Faculty, Basic Education
Department, 15030, Burdur, TURKEY Email: [email protected]
28
ACCEPTED MANUSCRIPT Table S1: Some optimized structure parameters of Compound B in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3944 1.3925 1.3876 1.4042 1.0851 1.4162 1.4065 1.3935 1.4992 1.3543 1.2113 1.2784 1.3612 1.4423 1.3180 1.0962 1.0927 1.0969 1.0097 1.3803 0.9759 1.2312 1.2305 0.9861
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 C18-H22 C18-H26 C18-H27 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 O19-H24
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(18-27) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(16,17,18,27) D(11,12,13,14)
N15-N16-H23 C14-O19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
117.4493 105.1650 114.8579 113.9151 105.9037 123.0208 124.8035
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-C18-H22 N16-C17-C18-H26 N16-C17-C18-H27 N11-N12-C13-C14
29
3.6340 52.3912 172.6033 -68.0954 1.8528
ACCEPTED MANUSCRIPT Table S2: Some optimized structure parameters of Compound C in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3946 1.3928 1.3878 1.4037 1.0849 1.4160 1.4104 1.3933 1.4989 1.3545 1.2121 1.2694 1.3737 1.4407 1.3235 1.0971 1.0924 1.0965 1.0098 1.3694 0.9759 1.2314 1.2308 1.0952 1.0951 1.0932
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 C18-H22 C18-H26 C18-H27 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 C19-H24 C19-H28 C19-H32
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-31) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(18-27) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24) R(19-28) R(19-32)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(16,17,18,27) D(11,12,13,14)
N15-N16-H23 C14-C19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
118.2519 110.9655 116.9023 112.6957 105.8490 122.9412 124.7125
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-C18-H22 N16-C17-C18-H26 N16-C17-C18-H27 N11-N12-C13-C14
30
4.0711 -68.7987 171.7885 51.4671 4.1556
ACCEPTED MANUSCRIPT Table S3: Some optimized structure parameters of Compound D in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3948 1.3951 1.3878 1.4038 1.0849 1.4191 1.4076 1.3901 1.5010 1.3534 1.2166 1.2764 1.3525 1.4434 1.3168 1.0099 1.0171 1.0084 1.3899 0.9760 1.2320 1.2320 1.0955 1.0952 1.0931
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 N18-H22 N18-H26 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 C19-H24 C19-H27 C19-H31
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24) R(19-27) R(19-31)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(11,12,13,14)
N15-N16-H23 C14-C19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
118.2543 110.8974 120.1289 110.9365 106.2298 122.5429 124.5635
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-N18-H22 N16-C17-N18-H26 N11-N12-C13-C14
31
3.8095 24.6336 171.8334 4.3309
ACCEPTED MANUSCRIPT Figure S1: FT-IR spectra of dyes
M AN U
SC
RI PT
Compound A
AC C
EP
TE D
Compound B
32
ACCEPTED MANUSCRIPT Figure S1: cont.
M AN U
SC
RI PT
Compound C
AC C
EP
TE D
Compound D
33
ACCEPTED MANUSCRIPT Figure S2: The measurement spectra of 1H-NMR for Compounds A, B and C.
AC C
EP
TE D
M AN U
SC
RI PT
Compound A
34
ACCEPTED MANUSCRIPT Figure S2: cont.
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ACCEPTED MANUSCRIPT Highlights
Four new azo dyes which have the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups have been synthesized.
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The DFT based on B3LYP hybrid functional with 6- 31G(d) basis set has been used to calculate the structural and vibrational properties of dyes.
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The vibrational frequencies of all synthesized compounds have been carried out with GAUSSVIEW 5.0.8 and the VEDA4 programs.
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The chemical shift calculations for 1H NMR and Invariant Atomic Orbital (GIAO) method.
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Experimental and theoretical results are compatible with each other.
C-NMR of azo dyes are done by using Gauge-
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S0022-2860(17)30396-4
DOI:
10.1016/j.molstruc.2017.03.107
Reference:
MOLSTR 23603
To appear in:
Journal of Molecular Structure
Received Date: 22 January 2017 Revised Date:
21 March 2017
Accepted Date: 29 March 2017
Please cite this article as: E. Karabacak Atay, M. Gökalp, S.E. Kart, T. Tilki, Mono azo dyes derived from 5-nitroanthranilic acid: Synthesis, absorption properties and DFT calculations, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.03.107. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Graphical Abstract: The synthetic scheme for the preparation of compound A-D.
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Mono Azo Dyes Derived From 5-Nitroanthranilic Acid: Synthesis, Absorption
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Properties and DFT Calculations
3 Çiğdem KARABACAK ATAY1, Merve GÖKALP2, Sevgi Özdemir KART3, Tahir TİLKİ2
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[email protected]
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Mehmet Akif Ersoy University, Education Faculty, Elementary Education Department, 15030, Burdur, Turkey 2
Süleyman Demirel University, Faculty of Science & Arts, Chemistry Department, 32260, Isparta, Turkey 3
PamukkaleUniversity, Faculty of Science & Arts, Physics Department, 20070, Denizli, Turkey
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Four new azo dyes: 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A), 2-[(3-hydroxy-5-
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methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic
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nitrobenzoic acid (C) and 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D) which have
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the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups are synthesized in this work.
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The structures and spectroscopic properties of these new azo dyes are characterized by using spectroscopic
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methods such as FT-IR, 1H-NMR, 13C-NMR and UV–vis. Their solvatochromic properties in chloroform, acetic
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acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO) are studied. Moreover, molecular
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structures and some spectroscopic properties of azo dyes are investigated by utilizing the quantum computational
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chemistry method based on Density Functional Theory (DFT) employing B3LYP hybrid functional level with 6-
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31G(d) basis set. It is seen that experimental and theoretical results are compatible with each other.
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(B),
2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-
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Keywords: Anthranilic acid, Heterocyclic dye, Spectroscopic property, Density Functional Theory.
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1. Introduction
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Azo compounds are, a class of chemical compounds, currently receiving attention in scientific and technological
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research [1-4]. These chemical materials are colored compounds which are yellow, red, orange, blue or even
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green, depending on the structure of the molecule. Azo compounds are important materials which are used in the
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different areas [5-13]. Especially, computational and structural researches on azo dyes have been interested in
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the fields of dye chemistry as well as in dye industry in recent years, because these studies have been carried out
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to reveal the structure-performance relationship of dyes [14-18]. In our previous works [19,20], we have
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investigated the structural and spectral properties of a series of disazo dyes and performed computational studies
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based on Density Functional Theory (DFT). Recently, Sener et. al [21] have synthesized disazo dye containing
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pyrazole skeleton and characterized its structure by using FT-IR, 1H NMR and
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coumarin based disazo dyes have been synthesized and their spectroscopic properties have been clarified by
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experimental as well as theoretical investigations carried out by Yıldırım et. al [22].
C NMR. A series of novel
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In this study, our main aim is to investigate the structure-performance relationship of some mono azo dyes which
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are synthesized by coupling cyclizated active methylene compounds such as malondinitrile, ethylacetoacetate,
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acetylacetone and 3-aminocrotononitrile with diazonium salts derived from anthranilic acid by performing
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experimental studies and computational calculations. FT-IR and H-NMR spectra of four new azo dyes are
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measured in order to obtain the chemical structural properties. The molecular structure, vibrational and NMR
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spectra of the azo dyes synthesized in this work are calculated by using DFT method with the basis set of 6-
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31G(d). Crystal structures such as bond length, bond angle and dihedral angles of azo dyes compounds
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considered in this work are identified by quantum computational method based on DFT.
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2.1. Synthesis of 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A)
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2 mmol of 5-nitroanthranilic acid is dissolved in hydrochloric acid (in 5 ml water). Then, the solution is cooled
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to 0-5oC with stirring. Sodium nitrite (2 mmol) in water (5 ml) is gradually added to this solution over 15 min
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period at 0-5oC while stirring. The reaction mixture is stirred for 2h at this temperature. The resulting diazonium
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salt solution is then added dropwise to a well-cooled and stirred solution of malononitrile (2 mmol) in sodium
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acetate (2 g) dissolves in 20 mL water. The pH is maintained at 4-6 through the coupling process by adding
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sodium acetate. Stirring is continued for 4h at 0-5oC. The precipitated products diluted with cold water (50 mL),
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filtered off, washed with water several times, and dried. The obtained product is recrystallized from DMF-H2O
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mixture. Hydrazine hydrate (0.5 mL) is added to a solution of this obtained product (3 mmol) in 20 ml ethanol.
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The reaction mixture is heated under reflux for 4-6h and then cooled at room temperature. Upon water being
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added, precipitate product is filtered, washed with water several times, and dried. The obtained product 2-[(3,5-
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diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A) is recrystallized from DMF-H2O mixture.
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2.2. Synthesis of 2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B)
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2-[(3-hydroxy-5-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (B) is synthesized by following
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procedure of 2-[(3,5-diamino-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (A). However, instead of
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malononitrile, ethylacetoacetate is used as an active methylene compound in the synthesis of compound (B).
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2.3. Synthesis of 2-[(3,5-dimethyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (C)
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The procedure followed to syhtesize the Compound A is used for the synthesis of 2-[(3,5-dimethyl-1H-pyrazol-
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4-yl)diazenyl]-5-nitrobenzoic acid (C), except for active methylene compound. Acetylacetone is used instead of
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malononitrile.
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2.4. Synthesis of 2-[(5-amino-3-methyl-1H-pyrazol-4-yl)diazenyl]-5-nitrobenzoic acid (D)
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The synthesize procedure of title Compound D is the same as that of Compound A. Only different point from the
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synthesis of Compound A is that 3-aminocrotononitrile is used as an active methylene compound in the synthesis
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of compound D.
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The synthesis schemes for the preparation of compounds A-D are given in Figure 1 as mentioned above.
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2.5. Experimental equipments
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IR spectra for new azo dyes are performed by Schimadzu IR Prestige-21 Fourier Transform-infrared (FT-IR)
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spectrophotometer. Nuclear magnetic resonance spectra of all synthesized compounds are assigned with Bruker
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Avance 125 MHz. All of the wavenumbers for new azo dyes synthesized in this work are measured with
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Schimadzu UV-1601 double beam spectrophotometer at the various concentrations. Melting points were
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recorded on an Smart SMP30 Stuart melting point apparatus.
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3. Computational method
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ACCEPTED MANUSCRIPT The DFT based on B3LYP hybrid functional with 6-31G(d) basis set is used to calculate the structural and
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vibrational properties of four new azo dyes which are synthesized in this work [23,24]. Theoretical calculations
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for new azo dyes are performed by utilizing the GAUSSIAN 09W package based on quantum chemical
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calculation techniques [25]. The DFT method is a powerful tool to satisfy performance in terms of the desired
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sensitivity, computation time and power [26]. The DFT calculations based on B3LYP level are much more
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sensitive results in predicting structural and electronic characteristics than Hartree-Fock (HF) methods [27]. The
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optimal structures of the new azo dyes are obtained by using the B3LYP/6-31G(d) level. The optimized
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geometric structures of the azo dyes compounds are given in Figure 2. Vibrational modes of the molecules
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considered in this work are calculated with the help of vibration spectrum analysis by following the optimized
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structure of azo dyes. The DFT method tends to overestimate the vibrational modes; therefore scaling factor
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(0.9613) has to be used to overcome the insufficiencies of the theoretical approximations used in the
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calculations. Therefore, the results are attained to agreement with the corresponding experimental data [28]. All
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of the wavenumbers for new azo dyes synthesized in this work are found to be positive, providing that a true
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minimum on the potential surface. The vibrational data obtained from theoretical studies are assigned with the
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GAUSSVIEW 5.0.8 and the VEDA4 programs [29,30]. The 1H-NMR chemical shift data for the new azo dyes
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are predicted by using the same level method considered in this work via the Gauge-Including Atomic Orbital
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(GIAO) method [31]. The 1H-NMR chemical shift calculations are analyzed by considering Tetramethylsilane
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(TMS) as a reference. UV-vis spectrum analyses of azo dyes considered in this work are studied by using Time
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Dependent Density Functional Theory (TD-DFT) employing B3LYP level with the basis set of 6-31G(d) in the
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different solvents.
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4. Results and discussion
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Physical properties of Compounds A-D were listed in Table 1. The determination of tautomerism is important,
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especially for theoretical studies, because of their different properties such as photo-physical, biological, thermal
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and technical. Compound B can exist in four possible tautomeric forms, namely, the azo-enol form, hydrazo-keto
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form, the azo-keto form and the hydrazo-enol form. The deprotonation of tautomeric forms of Compound B lead
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to common anions. Also, Compound A, C and D can exist in two possible tautomeric forms, namely, the azo
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form and the hydrazo form. Tautomeric forms of Compounds A-D are shown in Figure 3.
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shown in the figure indicate that as the transmittance is low, absorption is high. When any peaks are not
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observed in the figure, photons are not observed. Therefore, it can be said that Compound A has not a specific
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vibrations at the wavenumber considered. The FT-IR spectra of Compounds A-D shows aromatic (Ar–H) band
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at 3420–3280 cm−1, aliphatic (Alip–H) band at 3040–2880 cm−1 and azo (N=N) band at 1580–1480 cm−1. FT-IR
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spectra of dyes are given in Figure S1 (Supplementary data, Appendix A). As corresponding B3LYP/6-
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31G(d) predictions, aromatic (Ar-H) band is recorded within the region of 3129–3095 cm−1. The FT-IR spectra
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of aliphatic (Alip–H) and azo (N=N) bands are calculated as values of 2943–2931 cm−1 and at those of 1485–
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1425 cm−1, respectively. 84 normal modes of the vibrations are observed for Compound A; 29 modes are
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stretching vibrations, 28 modes are bending vibrations and the rest, 27 modes, are torsional vibrational for
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Compound A. As for Compound B, 84 normal modes of the vibrations are obtained. 29 modes of these
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vibrations are stretching vibrations, 28 modes are bending vibrations and 27 modes are torsional vibrations. The
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Compound C has 90 normal modes of the vibrations; 31, 30 and 29 modes of these are stretching vibration,
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bending vibration and torsional vibrations, respectively. Finally, the normal modes of the vibrations of
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Compound D are made up of 30 modes of stretching vibrations, 29 modes of bending vibrations and 28 modes of
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torsional vibrations. The vibrational frequencies produced by DFT method within 6-31G(d) basis set are
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multiplied by a scale factor of 0.9613 to match experimental vibrational frequencies [28]. The values of
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vibrational frequencies calculated by B3LYP/6-31G(d) method are given in Table 2, along with experimental
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data. It is seen that theoretical data are in good agreement with experimental results except for a few
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wavenumbers.
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The vibrational frequencies of all synthesized compounds are assigned with GAUSSVIEW 5.0.8 and the
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VEDA4 programs. The linear regression of Compound A between theoretical and experimental frequencies is
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shown in Figure 5. Linear regression is carried out by using the linear equation of ݔܽ = ݕ+ ܾ , where ܽ and ܾ
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are fit constants. The correlation between the experimental and the calculated frequencies multiplied by scale
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factor of Compound A is linear as shown in Figure 5. The equality of = ݕ1.0037 ݔ− 3.2699 (ܴ = 0.9998) is
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obtained by using the method of DFT/B3LYP. It can be concluded that the frequency values obtained from the
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method of DFT/B3LYP is consistent with the experimental data, since the slope goes to unity as shown in
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Figure 5. The correlation value (ܴ) is found as 0.9998.
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illustrated in Figure 6. The measurement spectra of 1H-NMR for Compounds A, B and C are given in Figure S2
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(Supplementary data, Appendix A). 1H-NMR chemical shift spectra of compounds show broad peaks between
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7.42 and 6.30 ppm (NH2), and between 15.92 and 11.21 ppm (NH) of pyrazole. The other chemical shift δ values
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of 8.74–7.53 ppm (aromatic H), 2.17-2.00 ppm (CH3) for pyrazole and 16.58–15.80 ppm (OH) for carboxylic
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acid are recorded.
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128.09 and 115.81 ppm were observed and assigned to pyrazole carbons (C17, C14 and C13) and 157.14,
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141.35, 120.42, 113.55, 113.23 and 111.76 ppm were observed and defined to phenyl carbons (C4, C1, C3, C2,
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C6 and C5) of Compound D. Also, 167.13 ppm was identified to carbonyl carbon (C8) and 9.87 ppm was
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assigned to methyl carbon (C19). The measurement spectra of 13C-NMR for Compounds A, B and C are given in
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Figure S3 (Supplementary data, Appendix A). The theoretical 1H and 13C NMR data are computed by using
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B3LYP/6-31G(d) in the gas phase. The 1H-NMR values calculated for Compounds A-D in the solvent of DMSO
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and corresponding experimental data are given in Table 3. As we consider the 1H-NMR values calculated by
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B3LYP/6-31G(d), the compounds show broad peaks between 4.79 and 3.08 ppm (NH2), and between 8.48 and
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6.51 ppm (NH) for pyrazole. The other chemical shift δ values of 8.12–7.19 ppm (aromatic H), 2.47-1.89 ppm
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(CH3) for pyrazole and 5.59–5.74 ppm (OH) for carboxylic acid are obtained. When compare the theoretical
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results and experimental data of 1H-NMR, except for X-H (-OH, NH), aromatic and aliphatic protons are in good
168
agreement with each other. It can be clearly seen that -OH and -NH protons resonate at the different regions in
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our theoretical studies. This indicates that the tautomerization occurs in these compounds. Experimental and
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theoretical chemical shifts give ones useful information about chemical structure of compounds. Comparison of
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general, the chemical shifts values of the aromatic carbons appear in the range of 100–160 ppm.
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UV-spectra analyses of compounds are investigated experimentally for five different solvents of DMF,
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methanol, acetic acid, chloroform and DMSO. Compounds A-D gave a single absorbance without shoulder in all
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solvents. Compounds A, B and C were the largest in DMSO when compared with other four solvents. Also,
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λmax values of Compounds A, B and C in DMF were larger than λmax in acetic acid, chloroform and methanol.
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Compound D was the largest in DMF. It was also observed that λmax values of Compounds A-D in methanol,
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acetic acid, DMSO and DMF were shifted bathochromically according to the λmax in chloroform. These results
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suggest that Compound B is present as an anionic form in DMSO and as a tautomeric form in DMF and as a
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different tautomeric form in chloroform, methanol and acetic acid. TD-DFT is also used to compute the UV-vis
H-NMR spectra of azo dyes synthesized in this work are measured and as an example, that of Compound D is
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C NMR resonances at 151.31,
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depends on the nature of the media. Therefore, absorption spectra of title compound in solvents with different
184
polarities are systematically investigated. UV spectrum analyses of compounds are listed in Table 5. Absorption
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spectrum of Compound A is shown in Figure 8. Due to solubility problems, absorption spectra are determined at
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various concentrations (10−6–10−8 M) between 300 and 700 nm. The UV–vis spectra shows that bathochromic
187
shifts of λmax values of compounds observed in DMSO and DMF are greater than those in the other solvents. On
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the other hand, the calculated λmax values of compounds do not show significant change in all solvents.
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Carbon-carbon and carbon-hydrogen bonds are the building blocks for organic compounds. In heteroatom-
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containing compounds, as well as these bonds, the bonds of heteroatoms with each other and with hydrogen are
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important. For this reason, the measurements of bond lengths and bond angles are indispensable for the
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theoretical studies of organic compounds. The optimized structure parameters values in the ground state for
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compound A are seen in Table 6. All the computed structural parameters for Compounds B, C and D are
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provided in the Table S1, S2 and S3 as a Supplementary material to compare with each other. Carbon-carbon
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bond length values for Compound A are computed in the between 1.3873 and 1.5009 Å by using DFT/B3LYP
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level with 6-31G(d). Nitrogen-nitrogen bond length value is found as 1.2837 Å for Compound A. Nitrogen-
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hydrogen bond length values for Compound A are in the between 1.0080 and 1.0164 Å. Oxygen-carbon-oxygen
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bond angle value of Compound A is 122.5176o while oxygen-carbon-oxygen-hydrogen dihedral angle value is
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computed as -3.5611o.
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5. Conclusion
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Four new azo dyes having the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups have
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been synthesized in this work. The structures and spectroscopic properties of azo dyes have been characterized
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by using spectroscopic methods such as FT-IR, 1H-NMR, 13C-NMR and UV–vis. Additionally, solvatochromic
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properties in chloroform, acetic acid, methanol, dimethylformamide (DMF) and dimethylsulphoxide (DMSO)
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have been studied. DFT method employing B3LYP level with 6-31G(d) basis set is also used to verify the
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molecular structure and spectroscopic properties of azo dyes synthesized in this study. The chemical shift
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calculations for 1H NMR and
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(GIAO) method. The positions of hydrogen and carbon atoms of molecules considered in this work are
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determined by means of computed 1H and 13C NMR chemical shifts. UV-vis spectrum analyses of all azo dyes
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C-NMR of azo dyes are carried out by using Gauge-Invariant Atomic Orbital
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by using both experimental and theoretical research on four new azo dyes considered in this work are performed
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for the first time. The theoretical data are compared with experimental values. The theoretical results and
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experimental data are in good agreement with each other. The experimental and theoretical comparisons are very
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useful to make correct assignment and to understand the basic vibrational, NMR spectra and molecular structure.
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This study also shows that DFT theory with B3LYP/6-31G(d) level calculations are powerful approach to
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investigate the structural and vibrational properties of azo dyes compounds. This study may be extended to study
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electronic properties of azo dyes by using DFT method in the future.
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Appendix A. Supplementary material
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Supplementary data associated with this article can be found, in the online version, at http://
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[17] A. Mahmood, M.H. Tahir, A. Irfan, A.G. Al-Sehemi, M.S. Al-Assiri, Heterocyclic azo dyes for dye sensitized solar cells: A quantum chemical Study, Comput. Theor. Chem. 1066 (2015) 94–99.
268
[18] H.F. Qian, T. Tao, Y.N. Feng, Y.G. Wang, W. Huang, Crystal structures, solvatochromisms and DFT
269
computations of three disperse azo dyes having the same azobenzene skeleton, J. Mol. Struct. 1123 (2016)
270
305-310.
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[19] Ç. Karabacak, O. Dilek, Synthesis, solvatochromic properties and theoretical calculation of some novel disazo indole dyes, J. Mol. Liq. 199 (2014) 227–236.
273
[20] Ç. Karabacak Atay, Y. Kara, M.Gökalp, I. Kara, T. Tilki, F. Karci, Disazo dyes containing pyrazole and
274
indole moieties: Synthesis, characterization, absorption characteristics, theoretical calculations, structural and
275
electronic properties, J. Mol. Liq. 215 (2016) 647–655.
277
[21] N. Sener, A. Bayrakdar, H.H. Kart, I. Sener, A combined experimental and DFT investigation of disazo dye having pyrazole skeleton, J. Mol. Struc. 1129 (2017) 222-230.
RI PT
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[22] F. Yıldırım, A. Demirçalı, F. Karcı, A. Bayrakdar, P. Tunay Taşlı, H.H. Kart, New coumarin-based disperse
279
disazo dyes: Synthesis, spectroscopic properties and theoretical calculations, J. Mol. Liq. 223 (2016) 557–
280
565.
282 283 284
[23] C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B. 37 (1988) 785-789.
M AN U
281
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[24] A. D. Becke, Density‐functional thermochemistry. III. The role of exact exchange, J. Chem. Phys. 98 (1993) 5648–5652.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V.
286
Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J.
287
Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
288
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M.
289
Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari,
290
A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N.J. Millam, M. Klene, J.E. Knox, J.B.
291
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi,
292
C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.
293
Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox,
294
Gaussian 09, Gaussian, Inc., Wallingford CT, 2009.
296
EP
AC C
295
TE D
285
[26] M.A. Palafox, N. Iza, M. Gil, The hydration effect on the uracil frequencies: an experimental and quantum chemical study, J. Mol. Struct. (Theochem.) 585 (2002) 69-92.
297
[27] M. Karakus, S. Solak, T. Hökelek, H. Dal, A. Bayrakdar, S. Özdemir Kart, M. Karabacak, H. H. Kart,
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Synthesis, crystal structure and ab initio/DFT calculations of a derivative of dithiophosphonates,
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Spectrochim. Acta A. 122 (2014) 582–590.
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[28] J.P. Merrick, D. Moran, L. Radom, An Evaluation of Harmonic Vibrational Frequency Scale Factors, J. Phys. Chem. A. 111 (2007) 11683-1170. [29] R. D. Dennington, T. A. Keith, J. M. Millam, GaussView 5.0.8, Gaussian Inc., 2008.
303
[30] M. H. Jamroz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004.
304
[31] R. Ditchfiled, Molecular Orbital Theory of Magnetic Shielding and Magnetic Susceptibility, J. Chem. Phys.
305
56 (1972) 5688–5691.
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302
306 307
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308 309 310
M AN U
311 312 313 314
318 319 320 321 322 323 324
EP
317
AC C
316
TE D
315
325 326 327 328 329
11
ACCEPTED MANUSCRIPT Figure Captions
331
Figure 1. The synthetic scheme for the preparation of Compounds A-D.
332
Figure 2. The calculated optimized structures of Compounds A-D at the level of DFT/B3LYP with the basis of
333
6-31G(d).
334
Figure 3. Tautomeric forms of Compounds A-D.
335
Figure 4. Transmittance versus wavenumber of Compound A computed from DFT/B3LYP method with 6-
336
31G(d) basis set.
337
Figure 5. The linear regression between the experimental and theoretical frequencies of Compound A.
338
Figure 6. 1H-NMR spectrum for Compound D.
339
Figure 7. 13C-NMR spectrum for Compound D.
340
Figure 8. The measurement absorption spectrum of Compound A.
342 343 344
349 350 351 352 353 354
EP
348
AC C
347
TE D
345 346
SC
M AN U
341
RI PT
330
355 356 357 358 359
12
ACCEPTED MANUSCRIPT 360
Figure 1.
SC
RI PT
361
M AN U
362 363 364 365 366
370 371 372 373 374 375 376
EP
369
AC C
368
TE D
367
377 378 379 380 381 13
ACCEPTED MANUSCRIPT 382
Figure 2.
RI PT
Compound A
M AN U
SC
Compound B
AC C
EP
TE D
Compound C
Compound D
383
14
ACCEPTED MANUSCRIPT
384
Figure 3.
Compound A
M AN U
SC
RI PT
Compound C
Compound D
AC C
EP
TE D
Compound B
15
ACCEPTED MANUSCRIPT Figure 4.
SC
RI PT
385
386
M AN U
387 388 389 390
394 395 396 397 398 399 400 401
EP
393
AC C
392
TE D
391
402 403 404 405 406 16
ACCEPTED MANUSCRIPT 407
Figure 5.
SC
RI PT
Experimental (cm-1)
408
M AN U
409 410
Calculated (cm-1)
411 412
416 417 418 419 420 421 422
EP
415
AC C
414
TE D
413
423 424 425 426 427
17
ACCEPTED MANUSCRIPT 428
Figure 6.
432 433 434 435 436
EP
431
AC C
430
TE D
M AN U
SC
RI PT
429
437 438 439 440 441 18
ACCEPTED MANUSCRIPT 442
Figure 7.
M AN U
SC
RI PT
443
447 448 449 450 451 452 453
EP
446
AC C
445
TE D
444
454 455 456 457 458
19
ACCEPTED MANUSCRIPT Figure 8.
M AN U
SC
RI PT
459
460 461
465 466 467 468 469 470 471
EP
464
AC C
463
TE D
462
472 473 474 475 476
20
ACCEPTED MANUSCRIPT Table Captions
478
Table 1. Physical properties of Compounds A-D.
479
Table 2. Comparison of FT-IR experimental values with those obtained from B3LYP/6-31G(d) method.
480
Table 3. Comparison of 1H-NMR experimental values with those calculated from DFT method.
481
Table 4. Comparison of 13C-NMR experimental values with those calculated from B3LYP/6-31G(d) method.
482
Table 5. The effect of solvent on λmax (nm) obtained by experimentally and theoretically for Compounds A-D.
483
Table 6. The structure parameters optimized in the ground state for Compound A; Bond length (Å), bond angle
484
(o) and dihedral angle (o).
RI PT
477
SC
485 486 487
M AN U
488 489 490 491
495 496 497 498 499 500 501
EP
494
AC C
493
TE D
492
502 503 504 505 506
21
ACCEPTED MANUSCRIPT 507
Table 1. Compound
Molecular formula
m.p. (oC) (colour)
(m. wt)
(%)
C10H9N7O4 (291.22)
275.7 (dark brown)
67
B
C11H9N5O5 (291.22)
285.4 (yellow)
86
C
C12H11N5O4 (289.25)
189.4 (dark yellow)
74
D
C11H10N6O4 (290.23)
218.6 (brown)
509
511
M AN U
512 513 514 515 516
522 523 524 525 526
EP
521
AC C
520
TE D
517
519
78
SC
510
RI PT
A
508
518
Yield
527 528 529 530 531 22
ACCEPTED MANUSCRIPT 532
Table 2. Vibrational frequencies (cm-1) Compound
(A)
Experiment
DFT/B3LYP*
νAr-H
νAlip-H
νN=N
νAr-H
νAlip-H
νN=N
3420
--
1580
3095 (C3-H30)
-
1466
3128 (C2-H29) (B)
3320
2960
1540
3095 (C3-H30)
2933 (C18-H22H26H27)
1485
3098 (C3-H31)
2931 (C18-H22H26H27)
1468
3127 (C6-H29)
2943 (C19-H24H28H32)
3128 (C6-H28) 3129 (C2-H29) 3280
2880
1520
SC
(C)
RI PT
3122 (C6-H28)
3129 (C2-H30) (D)
3320
3040
1480
3098 (C3-H30)
M AN U
3122 (C6-H28) 3129 (C2-H29)
533
*basis set 6-31G(d), scale factor 0.9613 [28]
534 535
539 540 541 542 543
EP
538
AC C
537
TE D
536
2943 (C19-H24H27H31)
23
1425
ACCEPTED MANUSCRIPT
Table 3. 1
H-NMR (d, ppm, DMSO-d6)
(A)
Aro-H
Alip-H
X-H
Aro-H
7.94-8.46 (m. 3H)
-
6.30 (pyrazole NH2)
-
7.42 (pyrazole NH2)
7.19-7.98 (m. 3H)
16.50 (OH)
7.94-8.62 (m. 3H)
2.17 (s. 3H pyrazole CH3)
2.00 (s. 6H pyrazole CH3)
11.44 (pyrazole NH)
3.15-4.33 (pyrazole NH2)
1.89-2.39 (s. 3H pyrazole CH3)
6.51 (pyrazole NH) 5.67 (OH) 7.82 (pyrazole NH)
15.80 (OH)
5.66 (OH)
11.21 (pyrazole NH)
7.50-8.12 (m. 3H)
7.38 (pyrazole NH2)
7.37-8.03 (m. 3H)
TE D
2.01 (s. 3H pyrazole CH3)
-
8.46 (pyrazole OH)
1.90-2.47 (s. 3H pyrazole CH3)
8.48 (pyrazole NH)
1.91-2.11 (s. 3H pyrazole CH3)
5.59 (OH)
1.72-2.01 (s. 3H pyrazole CH3)
3.29-4.56 (pyrazole NH2) 7.28 (pyrazole NH)
16.58 (OH)
5.74 (OH)
EP
15.92 (pyrazole NH)
AC C
7.53-8.71 (m. 3H)
3.08-4.79 (pyrazole NH2)
13.29 (pyrazole OH)
16.50 (OH) (D)
7.28-8.11 (m. 3H)
M AN U
(C)
7.98-8.74 (m. 3H)
X-H
-
SC
11.31 (pyrazole NH)
(B)
Alip-H
RI PT
Compound
DFT/B3LYP
24
ACCEPTED MANUSCRIPT
Table 4. Experimental
Chemical shift values of 13C-NMR* (ppm)
13C-NMR (DMSO-d6)
Compound B
Compound C
Compound D
Compound A
Compound B
Compound C
Compound D
157.50 (C8)
153.51 (C8)
154.21 (C8)
158.00 (C8)
168.79 (C8)
166.56 (C8)
169.53 (C8)
167.13 (C8)
145.55 (C4)
143.94 (C4)
145.48 (C4)
145.69 (C4)
156.49 (C4)
158.48 (C4)
154.14 (C4)
157.14 (C4)
134.03 (C17)
140.44 (C14)
136.12 (C17)
136.59 (C17)
152.77 (C17)
149.19 (C14)
145.05 (C17)
151.31 (C17)
131.14 (C14)
133.24 (C17)
132.83 (C1)
131.62 (C1)
144.64 (C14)
147.14 (C17)
135.22 (C1)
141.35 (C1)
131.02 (C1)
132.85 (C1)
127.94 (C14)
128.26 (C14)
143.58 (C1)
141.68 (C1)
129.28 (C14)
128.09 (C14)
113.54 (C3)
115.93 (C13)
125.56 (C13)
114.74 (C3)
130.20 (C3)
131.97 (C13)
127.89 (C13)
120.42 (C3)
113.53 (C2)
115.40 (C3)
116.52 (C3)
113.93 (C13)
126.17 (C2)
127.14 (C3)
122.79 (C3)
115.81 (C13)
112.35 (C6)
115.01 (C6)
114.46 (C6)
113.49 (C2)
125.77 (C6)
126.78 (C6)
115.98 (C6)
113.55 (C2)
110.83 (C5)
114.12 (C2)
113.70 (C2)
112.09 (C6)
120.59 (C5)
114.54 (C2)
114.04 (C2)
113.23 (C6)
106.81 (C13)
111.44 (C5)
110.72 (C5)
110.78 (C5)
115.94 (C13)
113.55 (C5)
95.35 (C5)
111.76 (C5)
1.55 (C18)
9.64 (C19)
11.78 (C18)
10.22 (C19)
9.87 (C19)
M AN U
TE D
AC C
*Reference: TMS B3LYP/6-311+G(2d,p) GIAO.
8.89 (C19)
EP
1.60 (C18)
SC
Compound A
RI PT
DFT/B3LYP
25
10.22 (C18)
ACCEPTED MANUSCRIPT Table 5. Experiment Compound
DMSO
DMF
B3LYP/B3LYP/6-31G(d)
Methanol
Acetic
Chloroform
DMSO
DMF
Methanol
Acid
Acetic
Chloroform
Acid
478
472
438
400
346
488
487
487
478
475
(B)
442
430
402
400
398
436
436
436
436
436
(C)
390
378
354
348
350
475
475
474
474
474
(D)
442
446
384
376
340
465
465
464
463
463
AC C
EP
TE D
M AN U
SC
RI PT
(A)
26
ACCEPTED MANUSCRIPT Table 6. DFT/ B3LYP/6-31G(d) 1.3952 1.3950 1.3873 1.4048 1.0851 1.4198 1.4042 1.3902 1.5009 1.3548 1.2156 1.2837 1.3414 1.4484 1.3205 1.0164 1.0102 1.0080 1.4038 0.9759 1.2324 1.2323 1.0105 1.0122
SC
RI PT
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 N18-H23 N18-H22 N16-H24 N15-N16 O9-H27 N7-O20 N7-O21 N19-H26 N19-H25
M AN U
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-23) R(18-22) R(16-24) R(15-16) R(9-27) R(7-20) R(7-21) R(19-26) R(19-25)
H22-N18-H23 N15-N16-H24 H25-N19-H26 N11-N12-C13 C4-N11-N12 C8-O9-H27 O9-C8-O10 O20-N7-O21
EP
AC C
A(22,18,23) A(15,16,24) A(25,19,26) A(11,12,13) A(4,11,12) A(8,9,27) A(9,8,10) A(20,7,21)
TE D
Bond Angles (º)
D(10,8,9,27) D(16,17,18,22) D(16,17,18,23) D(11,12,13,14)
115.4356 117.6179 117.9513 119.1514 111.2886 106.1096 122.5176 124.5213
Dihedral Angles (º) O10-C8-O9-H27 N16-C17-N18-H22 N16-C17-N18-H23 N11-N12-C13-C14
27
-3.5611 -26.1243 -170.7766 -3.9886
ACCEPTED MANUSCRIPT Appendix A Supplementary data for
Properties and DFT Calculations
RI PT
Mono Azo Dyes Derived From 5-Nitroanthranilic Acid: Synthesis, Absorption
1
Mehmet Akif Ersoy University, Education Faculty, Basic Education Department, 15030, Burdur, Turkey
Süleyman Demirel University, Faculty of Science & Arts, Chemistry Department, 32260, Isparta, Turkey PamukkaleUniversity, Faculty of Science & Arts, Physics Department, 20070, Denizli, Turkey
AC C
EP
TE D
3
M AN U
2
SC
Çiğdem KARABACAK ATAY1*, Merve GÖKALP2, Sevgi Ozdemir KART3, Tahir TİLKİ2
_____________________________________________ * Corresponding author, Mehmet Akif Ersoy University, Education Faculty, Basic Education
Department, 15030, Burdur, TURKEY Email: [email protected]
28
ACCEPTED MANUSCRIPT Table S1: Some optimized structure parameters of Compound B in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3944 1.3925 1.3876 1.4042 1.0851 1.4162 1.4065 1.3935 1.4992 1.3543 1.2113 1.2784 1.3612 1.4423 1.3180 1.0962 1.0927 1.0969 1.0097 1.3803 0.9759 1.2312 1.2305 0.9861
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 C18-H22 C18-H26 C18-H27 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 O19-H24
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(18-27) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(16,17,18,27) D(11,12,13,14)
N15-N16-H23 C14-O19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
117.4493 105.1650 114.8579 113.9151 105.9037 123.0208 124.8035
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-C18-H22 N16-C17-C18-H26 N16-C17-C18-H27 N11-N12-C13-C14
29
3.6340 52.3912 172.6033 -68.0954 1.8528
ACCEPTED MANUSCRIPT Table S2: Some optimized structure parameters of Compound C in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3946 1.3928 1.3878 1.4037 1.0849 1.4160 1.4104 1.3933 1.4989 1.3545 1.2121 1.2694 1.3737 1.4407 1.3235 1.0971 1.0924 1.0965 1.0098 1.3694 0.9759 1.2314 1.2308 1.0952 1.0951 1.0932
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 C18-H22 C18-H26 C18-H27 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 C19-H24 C19-H28 C19-H32
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-31) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(18-27) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24) R(19-28) R(19-32)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(16,17,18,27) D(11,12,13,14)
N15-N16-H23 C14-C19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
118.2519 110.9655 116.9023 112.6957 105.8490 122.9412 124.7125
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-C18-H22 N16-C17-C18-H26 N16-C17-C18-H27 N11-N12-C13-C14
30
4.0711 -68.7987 171.7885 51.4671 4.1556
ACCEPTED MANUSCRIPT Table S3: Some optimized structure parameters of Compound D in the ground state.
SC
RI PT
DFT/ B3LYP/6-31G(d) 1.3948 1.3951 1.3878 1.4038 1.0849 1.4191 1.4076 1.3901 1.5010 1.3534 1.2166 1.2764 1.3525 1.4434 1.3168 1.0099 1.0171 1.0084 1.3899 0.9760 1.2320 1.2320 1.0955 1.0952 1.0931
M AN U
Bond Length (Å) C1-C2 C1-C6 C2-C3 C3-C4 C3-H30 C4-C5 C4-N11 C5-C6 C5-C8 C8-O9 C8-O10 N11-N12 N12-C13 C13-C14 C14-N15 N18-H22 N18-H26 N16-H23 N15-N16 O9-H25 N7-O20 N7-O21 C19-H24 C19-H27 C19-H31
TE D
Parameters via Gaussian R(1-2) R(1-6) R(2-3) R(3-4) R(3-30) R(4-5) R(4-11) R(5-6) R(5-8) R(8-9) R(8-10) R(11-12) R(12-13) R(13-14) R(14-15) R(18-22) R(18-26) R(16-23) R(15-16) R(9-25) R(7-20) R(7-21) R(19-24) R(19-27) R(19-31)
Bond Angles (º)
AC C
EP
A(15,16,23) A(14,19,24) A(11,12,13) A(4,11,12) A(8,9,25) A(9,8,10) A(20,7,21)
D(10,8,9,25) D(16,17,18,22) D(16,17,18,26) D(11,12,13,14)
N15-N16-H23 C14-C19-H24 N11-N12-C13 C4-N11-N12 C8-O9-H25 O9-C8-O10 O20-N7-O21
118.2543 110.8974 120.1289 110.9365 106.2298 122.5429 124.5635
Dihedral Angles (º) O10-C8-O9-H25 N16-C17-N18-H22 N16-C17-N18-H26 N11-N12-C13-C14
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3.8095 24.6336 171.8334 4.3309
ACCEPTED MANUSCRIPT Figure S1: FT-IR spectra of dyes
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ACCEPTED MANUSCRIPT Figure S2: The measurement spectra of 1H-NMR for Compounds A, B and C.
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ACCEPTED MANUSCRIPT Figure S3: The measurement spectra of 13C-NMR for Compounds A, B and C.
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ACCEPTED MANUSCRIPT Highlights
Four new azo dyes which have the same 4-nitrobenzene/azo/pyrazole skeleton and different substituted groups have been synthesized.
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The DFT based on B3LYP hybrid functional with 6- 31G(d) basis set has been used to calculate the structural and vibrational properties of dyes.
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The vibrational frequencies of all synthesized compounds have been carried out with GAUSSVIEW 5.0.8 and the VEDA4 programs.
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The chemical shift calculations for 1H NMR and Invariant Atomic Orbital (GIAO) method.
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Experimental and theoretical results are compatible with each other.
C-NMR of azo dyes are done by using Gauge-
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