Electrochromic materials are of great interest for their potential in eyewear protection and data storage devices, as they change colors in response to electrochemical switching. While many of the systems currently used are based on inorganic materials, organic materials such as triazenes have emerged as viable alternatives due to their unique properties, including optical properties. Triazenes are a class of organic compounds with three consecutive nitrogen atoms in an acyclic arrangement, and they have been used for a variety of applications in medicinal and synthetic chemistry. However, the effects of solvents on the UV-visible absorption spectrum of triazenes have not been fully investigated. The neutral molecules of 3,3-diisopropyl-1-phenyltriazene and 1-(4-chlorophenyl)-3-cyclopentyltriazene in acetonitrile, the UV-visible spectra corresponded respectively to HOMO → LUMO transitions with a large maximum absorption at 299.74 nm (4.1364 eV) and 299.57 nm (4.1387 eV) and the most intense oscillator strength (f = 0.6988) and (f = 0.7372). These results suggest that the electronic transitions of the compounds are highly influenced by the nature of the substituents on the triazene unit, as well as the solvent used in the experiment. The redox couple 0.92 and -0.44 V/Ag/AgCl is attributed to the phenyl group. Compound III showed an oxidation and reduction peak respectively -0.27 and -0.8 V/Ag/AgCl attributed to the phenyl molecule. The study concluded that all three compounds were electroactive and exhibited reversible characteristics with oxidizing/reducing couples. This study aims to contribute to research on the optical properties of triazenes compounds and the application of quantum chemical calculation methods for understanding their molecular structures. By investigating the solute-solvent interactions occurring in the solvation shell of the solutes, we aim to gain insights into the effects of solvents on the UV-visible absorption spectrum of triazenes. Our findings may have implications for the development of functionalized triazenes as potential electrochromic materials.
Moore, J.S. (1997) Shape-Persistent Molecular Architectures of Nanoscale Dimension. Accounts of Chemical Research, 30, 402-413. https://doi.org/10.1021/ar950232g
Granqvist, C.G. (2000) Electrochromic Tungsten Oxide Films: A Review of Progress 1993-1998. Solar Energy Materials and Solar Cells, 60, 201-262. https://doi.org/10.1016/S0927-0248(99)00088-4
Niklasson, G.A. and Granqvist, C.G. (2007) Electrochromics for Smart Windows: Thin Films of Tungsten Oxide and Nickel Oxide, and Devices Based on These. Journal of Materials Chemistry, 17, 127-156. https://doi.org/10.1039/B612174H
Argun, A.A., et al. (2004) Multicolored Electrochromism in Polymers: Structures and Devices. Chemistry of Materials, 16, 4401-4412. https://doi.org/10.1021/cm049669l
Mortimer, R.J. (1997) Electrochromic Materials. Chemical Society Reviews, 26, 147-156. https://doi.org/10.1039/cs9972600147
Lampert, C.M. (1984) Electrochromic Materials and Devices for Energy Efficient Windows. Solar Energy Materials, 11, 1-27. https://doi.org/10.1016/0165-1633(84)90024-8
Monk, P.M., Mortimer, R.J. and Rosseinsky, D.R. (2007) Electrochromism and Electrochromic Devices. Cambridge University Press, Cambridge. https://doi.org/10.1017/CBO9780511550959
Chen, B., et al. (2005) Molecular Grafting to Silicon Surfaces in the Air Using Organic Triazenes as Stable Diazonium Sources and HF as a Constant Hydride-Passivation Source. Chemistry of Materials, 17, 4832-4836. https://doi.org/10.1021/cm051104h
Kimball, D.B. and Haley, M.M. (2002) Triazenes: A Versatile Tool in Organic Synthesis. Angewandte Chemie International Edition, 41, 3338-3351. https://doi.org/10.1002/1521-3773(20020916)41:18 3.0.CO;2-7
Sadtchikova, E.V. and Mokrushin, V.S. (2002) Interaction of Diazoimidazoles and Their Diazonium Salts with Primary and Secondary Amines. Mendeleev Communications, 12, 70-72. https://doi.org/10.1070/MC2002v012n02ABEH001570
Kirk, K.L. (1978) Facile Synthesis of 2-Substituted Imidazoles. The Journal of Organic Chemistry, 43, 4381-4383. https://doi.org/10.1021/jo00416a033
Seck, I., et al. (2020) Access to a Library of 1, 3-Disubstituted-1, 2, 3-Triazenes and Evaluation of Their Antimicrobial Properties. Current Topics in Medicinal Chemistry, 20, 713-719. https://doi.org/10.2174/1568026620666200127143005
Rouzer, C.A., et al. (1996) Oxidative Metabolism of 1-(2-Chloroethyl)-3-Alkyl-3-(Methyl Carbamoyl) Triazenes: Formation of Chloroacetaldehyde and Relevance to Biological Activity. Chemical Research in Toxicology, 9, 172-178. https://doi.org/10.1021/tx9500639
Moore, J.S., Weinstein, E.J. and Wu, Z. (1991) ChemInform Abstract: A Convenient Masking Group for Aryl Iodides. ChemInform, 23, 2465-2466. https://doi.org/10.1002/chin.199212103
Nicolaou, K., et al. (1999) Total Synthesis of Vancomycin—Part 2: Retrosynthetic Analysis, Synthesis of Amino Acid Building Blocks and Strategy Evaluations. Chemistry—A European Journal, 5, 2602-2621. https://doi.org/10.1002/(SICI)1521-3765(19990903)5:9 3.0.CO;2-X
Wirschun, W., Winkler, M., Lutz, K. and Jochims, J.C. (1998) 1, 3-Diaza-2-Azoniaallene Salts: Cycloadditions to Alkynes, Carbodiimides and Cyanamides. Journal of the Chemical Society, Perkin Transactions 1, No. 11, 1755-1762. https://doi.org/10.1039/a801797b
Wirschun, W. and Jochims, J.C. (1997) 1, 3-Diaza-2-Azoniaallene Salts, Novel N3-Building Blocks: Preparation and Cycloadditions to Olefins. Synthesis, No. 2, 233-241. https://doi.org/10.1055/s-1997-1161
Wirschun, W., Maier, G.M. and Jochims, J.C. (1997) On the Reaction of 1, 3-Diaza-2-Azoniaallene Salts with 1, 3-Butadienes and Cumulenes. Tetrahedron, 53, 5755-5766. https://doi.org/10.1016/S0040-4020(97)00283-4
Jones, L., Schumm, J.S. and Tour, J.M. (1997) Rapid Solution and Solid Phase Syntheses of Oligo (1, 4-Phenylene Ethynylene) s with Thioester Termini: Molecular Scale Wires with Alligator Clips. Derivation of Iterative Reaction Efficiencies on a Polymer Support. The Journal of Organic Chemistry, 62, 1388-1410. https://doi.org/10.1021/jo962336q
Gross, M.L., Blank, D.H. and Welch, W.M. (1993) The Triazene Moiety as a Protecting Group for Aromatic Amines. The Journal of Organic Chemistry, 58, 2104-2109. https://doi.org/10.1021/jo00060a028
Jian, H. and Tour, J.M. (2005) Preparative Fluorous Mixture Synthesis of Diazonium-Functionalized Oligo (Phenylene Vinylene) s. The Journal of Organic Chemistry, 70, 3396-3424. https://doi.org/10.1021/jo048051s
Stebani, J., Nuyken, O., Lippert, T. and Wokaun, A. (1993) Synthesis and Characterization of a Novel Photosensitive Triazene Polymer. Die Makromolekulare Chemie, Rapid Communications, 14, 365-369. https://doi.org/10.1002/marc.1993.030140607
Jollimore, J.V., Vaughan, K. and Hooper, D.L. (1996) 1-Aryl-3-(Carbamoyl Methyl) Triazenes: Synthesis, Spectroscopic Analysis and Cyclization to New 1, 2, 3-Benzotriazoles. The Journal of Organic Chemistry, 61, 210-214. https://doi.org/10.1021/jo951279i
Day, B.F., Campbell, T.W. and Coppinger, G. (1951) The Absorption Spectra of Some Aromatic Triazenes. Journal of the American Chemical Society, 73, 4687-4688. https://doi.org/10.1021/ja01154a059
Somani, P.R. and Radhakrishnan, S. (2003) Electrochromic Materials and Devices: Present and Future. Materials Chemistry and Physics, 77, 117-133. https://doi.org/10.1016/S0254-0584(01)00575-2
Zakerhamidi, M., et al. (2010) Substituent and Solvent Effects on the Photo-Physical Properties of Some Coumarin Dyes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 77, 337-341. https://doi.org/10.1016/j.saa.2009.12.060
Julliard, M. and Vernin, G. (1981) Biological Properties of Antitumor Triazenes. Industrial & Engineering Chemistry Product Research and Development, 20, 287-296. https://doi.org/10.1021/i300002a011
Casida, M.E., et al. (1998) Molecular Excitation Energies to High-Lying Bound States from Time-Dependent Density-Functional Response Theory: Characterization and Correction of the Time-Dependent Local Density Approximation Ionization Threshold. The Journal of Chemical Physics, 108, 4439-4449. https://doi.org/10.1063/1.475855
Lee, C., Yang, W. and Parr, R.G. (1988) Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Physical Review B, 37, 785-789. https://doi.org/10.1103/PhysRevB.37.785
Godbout, N., et al. (1992) Optimization of Gaussian-Type Basis Sets for Local Spin Density Functional Calculations. Part I. Boron through Neon, Optimization Technique and Validation. Canadian Journal of Chemistry, 70, 560-571. https://doi.org/10.1139/v92-079
Frisch, M., et al. (2009) Gaussian 09, Revision d. 01. Gaussian. Inc., Wallingford. https://gaussian.com/
Kuzin, Y.I., et al. (2020) Electrochemical Behaviour of the Monomeric and Polymeric Forms of N-Phenyl-3-(Phenylamino)-3H-Phenothiazine-7-Amine. Electrochimica Acta, 345, Article ID: 136195. https://doi.org/10.1016/j.electacta.2020.136195
Imato, K., et al. (2019) Synthesis, Photophysical and Electrochemical Properties of Pyridine, Pyrazine and Triazine-Based (D-π-)2A Fluorescent Dyes. Beilstein Journal of Organic Chemistry, 15, 1712-1721. https://doi.org/10.3762/bjoc.15.167