Visible absorption of the dyes (
This chapter provides a general overview and information on near-infrared (NIR) absorbing azo dyes. In this work, we have developed an efficient and simple protocol for the synthesis of novel A-π-D-π-A NIR azo dyes. The near-infrared absorbing azo dyes were synthesized by using 2-hydroxy-1,4 naphthoquinone (Lawsone) and different substituted aromatic primary amines. Furthermore, author developed push-pull chromophores of A-π-D-π-A type containing an electron-withdrawing azo core, phenazine moieties, and a hydroxyl group as electron donor. The benzo[a]quinoxalino[2,3-i]phenazin-5-ol moiety was introduced to make the system planer as well as to increase the π-conjugation. The optical properties of these dyes were studied in N,N-dimethylformamide (DMF).
- NIR absorbing azo dyes
- optical properties
- phenazine core
In 1856, William Henry Perkin accidentally discovered the world’s first commercially successful synthetic dye. Dyes are defined as colored organic or inorganic compounds, mixtures, complexes, or substances that once applied to the fibers/substrate, it imparts a permanent color to the fibers/substrate. This is able to resist fading upon exposure to sweat, light, water, and many chemicals, including oxidizing agents and microbial attack. Over 10,000 synthetic dyes were developed and used in manufacturing by the end of the nineteenth century. Azo dyes are a class of compounds containing a
Azo colorant represents the greatest production volume in dyestuff chemistry due to simplicity of coupling reaction, adaption to the needs of most diverse applications such as textile dying, coloring of plastics and polymer, in liquid crystal displays (LCD), optical data storage, nonlinear optics, biological and medical field, and advanced application in organic synthesis [4, 5, 6]. Azo chromophores have versatile applicability ranging from textile dyeing , leather dyeing , coloring of plastics, and polymer  to advanced applications such as liquid crystal displays , biological and medical studies, and advanced application in the organic synthesis . Also, they contribute greatest production volume of the dyestuff industry due to simplistic mode of their synthesis with high yield.
The infrared wavelength ranges of the electromagnetic spectrum cover the area between the visible region and the microwave region. The infrared radiation spectrum is generally accepted and can be subclassified into the near-, medium-, and far-infrared regions. An important challenge in creating molecules with desired optical properties lies in achieving a well-defined architecture while maintaining adequate electron density throughout the whole molecule . Organic materials with intense absorptions in the near-IR region (i.e., 750–1300 nm) are particularly important in number of applications including thermal imaging, optical data storage, automatic identification, etc. NIR absorbing dyes have been attracting increasing interest due to the rapid progress achieved in their high technology applications.
In this region, infrared radiation provides sufficient energy to the NIR dyes, which impart a
The planar structure of phenazine with a heterocyclic pyrazine nucleus and a fully conjugated aromatic π-system imparts to that special optical and redox properties. The optical properties give it functional for applications in molecular imaging as fluorescent tracers and stains for subcellular components and biological events. Highly electron-rich and redox-active molecules like phenazines might be functional for preparation of organic materials that includes donor-π-acceptor design. Pyrazine compounds are electron-deficient species. Hence, they are used in the design of n-type organic semiconductors; examples are pyrazinoquinoxaline derivatives, hexaazatriphenylenes, diquinoxalino, phenazine, and quinoxalinophenanthro phenazine . Richards et al. have shown that pyrazinacenes are good candidates as materials for organic thin film transistors as shown in the Figure 1 . The existence of a donor-π-acceptor (D-π-A) alternating structure has been proved to be an efficient way to reduce band gap energies of conjugated molecules. The phenazine core consists of the electron-withdrawing pyrazine ring which might be an excellent charge acceptor.
There are no further reports in the use of 2-hydroxy-1,4-naphthoquinone in the synthesis of azo colorants. It is known that the molecule with a quinoid fragment shows keto-enol tautomerism when a hydroxyl group is presenting adjacent to one of the quinoid carbonyl groups: the p-quinoid structure can transform into an
The reactions of 2-hydroxy-1,4-naphthoquinone in the synthesis of azo colorants for NIR-absorbing dyes have been explored in our previous work. Three different kinds of near-infrared (NIR) absorbing pull-push acceptor-π-donor-π-acceptor (A-π-D-π-A) V-shaped chromophoric dyes have been synthesized. These dyes are architect by doing substitution with 5-hydroxy and 6-arylazonium on the benzo[a]naphtho[2,3-h] phenazine dione core. Phenazine and anthraquinone moieties were envisaged in a single molecule with a view to enhance the photophysical properties in NIR region as shown in Figure 3 .
This work is aimed at synthesizing novel molecules containing both phenazine and azo cores that were envisaged in a single molecule with a view to enhance the photophysical properties in the NIR region. In this study, we have extended our contribution to synthesis NIR absorbing dyes (
2. Result and discussion
2.1 Synthesis strategy
In the present study, the use of 2-hydroxy-1,4-naphthoquinone (Lawsone)
In this context, authors have extended our contribution to synthesis of three different kinds of near infrared (NIR) absorbing pull-push acceptor–π–donor–π acceptor (A–π–D–π–A) chromophoric dyes. The NIR absorbing dyes (
The scaffold of phenazine,
2.2 Optical properties
The UV-visible absorption spectra of the dyes
|Dye||λmax (nm)||(log Ɛ)||Ɛmax (dm3 mol−1 cm−1)|
3. Experimental sections
3.1 General experimental procedure of the azo dyes (18–20)
The aromatic primary amines (5 g) was partially dissolved in conc. HCl (5 mL) in 80 mL water and cooled to 0–5°C . The solution of NaNO2 (2 g) in 5 mL water was added slowly to the reaction mixture, and the reaction temperature was kept below 5°C. The resulting aryl diazonium salt was added to the alkaline solution of Lawson (5 g) and NaOH (1.15 g) in 60 mL of water, and reaction temperature was maintained at 0–5°C. The reaction mass was stirred for 2.0–2.5 h, after which mixture was acidified with dil. HCl. The precipitate was settled down and filtered, washed with water and then with aqueous EtOH, and was dried.
3.2 General experimental procedure of the azo-phenazine dyes (12–14)
Diketo-azo derivatives (
3.3 General experimental procedure of 2,3-diaminophenazine (21)
3.4.1 6-(Phenyldiazenyl)benzo[a]quinoxalino[2,3-i]phenazin-5-ol (12)
Yield 72%; melting point (measured) >300°C.
FT-IR (KBr, cm−1) = 3057 (O–H), 1630 (C=N), 1589 (arom.), 1534 (arom. ring).
1H-NMR (DMSO, 500 MHz) = δ 8.30–8.24 (m, 4H, aromatic), 8.26–8.16 (m, 3H, aromatic), 7.92–7.76 (m, 8H, aromatic), 5.2 (1H, s, OH).
3.4.2 6-((4-(Dimethylamino)phenyl)diazenyl)benzo[a]quinoxalino[2,3-i]phenazin-5-ol (45)
Yield 80%, melting point (measured) >300°C. FT-IR (KBr, cm−1) = 3169 (O–H), 1674 (C=N), 1633 (arom.), 1514 (arom. ring). 1H-NMR (DMSO, 500 MHz) = δ 8.25 (s, 2H, aromatic), 8.23–7.78 (m, 12H, aromatic), 3.86 (s, 6H, CH3–N–CH3), 6.18 (1H, s, OH).
3.4.3 2-((5-Hydroxybenzo [a]quinoxalino[2,3-i]phenazin-6 yl)diazenyl)anthracene-9,10-dione (46)
Yield 67%, melting point (measured) >300°C. FT-IR (KBr, cm−1) = 3059 (O–H), 1629 (C=N), 1590 (arom.), 1529 (arom. ring). 1H-NMR (DMSO, 500 MHz) = δ 8.304 (s, 2H, aromatic), 8.292 (m, 12H, aromatic), 7.77–7.76 (m, 3H, aromatic), 5.2 (1H, s, OH).
Azo colorants represent the greatest production volume in dyestuff chemistry due to simplicity of coupling reaction, adaption to the needs of most diverse applications such as textile dying, coloring of plastics and polymer, in liquid crystal displays (LCD), optical data storage, nonlinear optics, biological and medical field, and advanced application in organic synthesis. In this context, authors have designed and developed push-pull chromophores of A-π-D-π-A type containing an electron-withdrawing azo core, phenazine moieties, and a hydroxyl group as electron donor. The benzo[a]quinoxalino[2,3-i]phenazin-5-ol moiety was introduced to make the system planer as well as to increase the п-conjugation. These synthesized chromophores were confirmed by FT-IR, 1H-NMR, 13C-NMR, and MS spectral analysis. The optical properties of these dyes were studied in DMF. NIR absorbing dyes have been considered in numerous recent hi-tech applications like optical device, optical recordings, laser printings, laser thermal writing displays, infrared photography, and biological/medical applications. In optoelectronic application areas, especially, NIR absorbing dyes are being developed and new structural designs of the dye chromophore molecules are being studied. Azo dyes are the most important class of organic dyes, but many of azo dyes suspect to be carcinogenic in nature. Therefore, the research of the dyes is aimed at development of new type of chromophores. The NIR azo dyes may probably prove to be a solution to this problem.
5. Future trends
There is an excellent range of organic compounds that absorb intensively higher than 700–1300 nm owing to electronic excitation. The basic acyclic NIR chromophores (polymethine dyes) as well as the basic cyclic NIR chromophores (annulenes, porphyrines, and tetraazaporphyrins) are well recognized. Structurally, more advanced NIR dyes with some meropolymethinic, quinonoid, and/or indigoid character will eventually be found. Color structure relationships are at present better well-known and more reliably predictable for closed shell than for open shell systems.
On account of their special optical properties, there exists scope for further research into designing small molecules bearing donor and acceptor functional groups directly attached to the phenazine nucleus that could possess NIR optical spectra, which would be sensitive to presence of solution analytes such as cations/anions as well as to pollutants such as polycyclic aromatic hydrocarbons and nitroaromatics. Additionally, preparation of more examples of phenazine-based low-band gap-containing molecules will also enhance its use in the field of organic photovoltaics.
Author is grateful to IntechOpen Publishers for being given the chance for contributory to the present book. This work was supported by Institute of Chemical Technology, Mumbai, India.
The authors declare no competing financial interest.
Li Y, Patrick BO, Dolphin D. Near-infrared absorbing azo dyes: Synthesis and X-ray crystallographic and spectral characterization of monoazopyrroles, bisazopyrroles, and a boron–azopyrrole complex. The Journal of Organic Chemistry. 2009; 74:5237-5243. DOI: 10.1021/jo9003019
Singh RP, Singh PK, Singh RL. Role of azoreductases in bacterial decolorization of azo dyes. Current Trends in Biomedical Engineering & Biosciences. 2017; 9:1-3. DOI: 10.19080/CTBEB.2017.09.555764
Telke A, Kalyani D, Jadhav J, Govindwar. Kinetics and mechanism of reactive red 141 degradation by a bacterial isolate Rhizobium radiobacterMTCC 8161. Acta Chimica Slovenica. 2008; 55:320-329
Arslanoglu Y, Sevim AM, Hamuryudan E, Gul A. Near-IR absorbing phthalocyanines. Dyes and Pigments. 2006; 68:129-132. DOI: 10.1016/j.dyepig.2005.01.019
Saratale RG, Saratale GD, Chang JS, Govindwar SP. Bacterial decolorization and degradation of azo dyes: A review. Journal of the Taiwan Institute of Chemical Engineers. 2011; 42:138-157. DOI: 10.1016/j.jtice.2010.06.006
Gregory P. In: Hunger K, editor. Industrial Dyes: Chemistry, Properties and Applications. Weinheim: Wiley-VCH; 2002. pp. 543-585
Bamfield P, Hutchings MG. Chromic Phenomena: Technological Applications of Colour Chemistry. 2nd ed. Cambridge: RSC; 2010
Koh J, Greaves AJ. Synthesis and application of an alkali-clearable azo disperse dye containing a fluorosulfonyl group and analysis of its alkali-hydrolysis kinetics. Dyes and Pigments. 2001; 50:117-126. DOI: 10.1016/S0143-7208(01)00028-6
Vijayaraghavan R, Vedaraman N, Surianarayanan M, MacFarlane DR. Extraction and recovery of azo dyes into an ionic liquid. Talanta. 2006; 69:1059-1062. DOI: 10.1016/j.talanta.2005.12.042
Fleischmann C, Lievenbrück M, Ritter H. Polymers and dyes: Developments and applications. Polymer. 2015; 7:717-746. DOI: 10.3390/polym7040717
Gouda MA, Eldien HF, Girges MM, Berghot MA. Synthesis and antitumor evaluation of thiophene based azo dyes incorporating pyrazolone moiety. Journal of Saudi Chemical Society. 2016; 20:151-157. DOI: 10.1016/j.jscs.2012.06.004
Nejati K, Rezvani Z, Seyedahmadian M, Seyedahmadian M. The synthesis, characterization, thermal and optical properties of copper, nickel, and vanadyl complexes derived from azo dyes. Dyes and Pigments. 2009; 83:304-311. DOI: 10.1016/j.dyepig.2009.05.007
Dong M, Babalhavaeji A, Hansen MJ, Kalman L, Woolley GA. Red, far-red, and near infrared photoswitches based on azonium ions. Chemical Communications. 2015; 51:12981-12984. DOI: 10.1039/C5CC02804C
Salvador MA, Reis LV, Almeida P, Santos PF. Delocalized cationic azo dyes containing a thiazole moiety. Tetrahedron. 2008; 64:299-303. DOI: 10.1016/j.tet.2007.11.004
Mikroyannidi J, Tsagkournos D, Sharma S, Kumar A, Vijay Y, Sharma G. Efficient bulk heterojunction solar cells based on low band gap bisazo dyes containing anthracene and/or pyrrole units. Solar Energy Materials and Solar Cells. 2010; 94:2318-2327. DOI: 10.1016/j.solmat.2010.08.001
Fuxin H, Yiqun W, Donghong G, Fuxi G. Synthesis, spectroscopic and thermal properties of nickel (II)eazo complexes with blue-violet light wavelength. Dyes and Pigments. 2005; 66:77-82. DOI: 10.1016/j.dyepig.2004.08.013
Knischka R, Lehmann U, Stadler U, Mamak M, Benkhoff J. Novel approaches in NIR curing technology. Progress in Organic Coating. 2009; 64:171-174. DOI: 10.1016/j.porgcoat.2008.09.015
Sekar N, Raut R, Umape P. Near infrared absorbing iron-complexed colorants for photovoltaic applications. Materials Science and Engineering B. 2010; 168:259-262. DOI: 10.1016/j.mseb.2010.01.018
Lamnatou C, Chemisana D. Solar radiation manipulations and their role in greenhouse claddings: Fresnel lenses, NIR- and UV-blocking materials. Renewable and Sustainable Energy Reviews. 2013; 18:271-287. DOI: 10.1016/j.rser.2012.09.041
Li N, J L, Li H, Kang E. Nonlinear optical properties and memory effects of the azo polymers carrying different substituents. Dyes and Pigments. 2011; 88:18-24. DOI: 10.1016/j.dyepig.2010.04.010
Salvador M, Almeida P, Reis L, Santos P. Near-infrared absorbing delocalized cationic azo dyes. Dyes and Pigments. 2009; 82:118-123. DOI: 10.1016/j.dyepig.2008.12.003
Kaur P, Sareen D. The synthesis and development of a dual-analyte colorimetric sensor: Simultaneous estimation of Hg2+ and Fe3+. Dyes and Pigments. 2011; 88:296-300. DOI: 10.1016/j.dyepig.2010.07.012
So B, Kim H, Lee S, Song H, Park J. Novel bent-shaped liquid crystalline compounds: IV. Dimesogenic compounds containing 2-hydroxy-1,3-dioxypropylene and azobenzene mesogens. Dyes and Pigments. 2006; 70:38-42. DOI: 10.1016/j.dyepig.2005.04.006
Tsai P, Wang I. A facile synthesis of some new pyrazolo[1,5-a]pyrimidine heterocyclic disazo dyes and an evaluation of their solvatochromic behavior. Dyes and Pigments. 2007; 74:578-584. DOI: 10.1016/j.dyepig.2006.03.022
Karcı F, Karcı F. The synthesis and solvatochromic properties of some novel heterocyclic disazo dyes derived from barbituric acid. Dyes and Pigments. 2008; 77:451-456. DOI: 10.1016/j.dyepig.2007.07.009
Yazdanbakhsh R, Mohammadi A, Abbasnia M. Some heterocyclic azo dyes derived from thiazolyl derivatives; synthesis; substituent effects and solvatochromic studies. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy. 2010; 77:1084-1087. DOI: 10.1016/j.saa.2010.08.079
Ucar M, Polat K, Solak A, Toyc M, Aksu M. The electrochemical behaviour of 20-halogenated derivatives of 4-methoxyazobenzene at a mercury electrode. Dyes and Pigments. 2010; 87:55-61. DOI: 10.1016/j.dyepig.2010.02.004
Wang D, He Y, Deng W, Wang X. The photoinduced surface-relief-grating formation behavior of side-chain azo polymers with narrow Mr distribution. Dyes and Pigments. 2009; 82:286-292. DOI: 10.1016/j.dyepig.2009.01.012
Zollinger H. Color chemistry. In: Syntheses, Properties, and Applications of Organic Dyes and Pigments. 3rd ed. Zurich: Verlag Helvetica Chimia Acta, Wiley VCH; 2003
Banerjee S. Phenazines as chemosensors of solution analytes and as sensitizers in organic photovoltaics. ARKIVOC. 2016; i:82-110. DOI: 10.3998/ark.5550190.p009.347
Richards G, Hill JP, Subbaiyan N, D’Souza F, Paul A, Mark K, et al. Pyrazinacenes: Aza analogues of acenes. The Journal of Organic Chemistry. 2009; 74:8914-8923. DOI: 10.1021/jo901832n
Romanyuk AL, Polishchuk OP, Litvin BL, Ganushchak N, Russ I. Synthesis and transformations of 2-hydroxy-3-arylazo-1,4-naphthoquinones. Journal of General Chemistry. 2002; 72:251-254. DOI: 10.1023/A:1015429803432
Choudhary A, Patil S, Sekar N. Solvatochromism, halochromism, and azo-hydrazone tautomerism in novel V-shaped azo-azine colorants—Consolidated experimental and computational approach. Coloration Technology. 2016; 132:1-12. DOI: 10.1111/cote.12226
Mei L, Tai LS, Tao FH, Jie S, Rong QL. A novel synthesis of 2,3-diaminophenazine. Research on Chemical Intermediates. 2012; 38:499-505. DOI: 10.1007/s11164-011-0366-z