Computational investigation on the ground state properties of trans-azobenzene and four kinds of hydroxy-ended azobenzene-type chromophores containing different substituent groups as electron donor and acceptor in different solvent media was carried out. The effects ofsubstituents –I2, -OH- and -CH3, -NH2, and –Cl2 on the electronic properties like the EHOMO, ELUMO, band gap, dipole moments, global hardness, electrophilicity indices were studied using the Ab initio restricted DFT self-consistent field method with the Becke Three Lee Yang Parr (B3LYP)/6-31G* method in vacuum, water, diethylether, ethanol and acetone. The results showed that these properties were altered upon substitution with different groups. The azobenzene gave a slight difference in its band gap in different solvent changing from (3.95 eV) in vacuum to the lowest (3.87 eV) in acetone but changes drastically as we introduce different substituents. It was also found that the dipole moment (μ), polarizability (α), absorption wavelength (λab) gave slight change in different solvents but rapidly increased as the band gap reduces, invoking their reactivities. They are also red-shifted as different substituents are added. Of all the studied molecules, compound H gave the lowest band gap of 0.46 eV, the highest dipole moment (875.02 D), the highest polarizability (64.97C.m2V-1) and it is the most red-shifted (401.13 nm). Molecule H therefore, has the lowest band gap, highest polarizability and dipole moment. It also has the highest molecular size and the highest planarity. This means that the molecule is the most reactive, most polarizable, highest electro-optic response and it is the softest.
| Published in | International Journal of Computational and Theoretical Chemistry (Volume 3, Issue 6) |
| DOI | 10.11648/j.ijctc.20150306.12 |
| Page(s) | 50-57 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2024. Published by Science Publishing Group |
Molecular Structure, Azobenzene, Solvent Effects, Band Gap, Ab initio Restricted Hf-Dft Self-Consistent Field Calculations, Dipole Moment
| [1] | Salem AH, Jordan Journal of Chemistry. (2) 2007, 133-144. |
| [2] | Armstrong GR, Clarkson J and Smith WEW, Journal. Phys. Chem. (99) 1995, 17825-17831. |
| [3] | Hosseinnezhad M, Khosravi A, Garanjig K and Moradian S, The comparison of spectra and dyeing properties of new azonaphthalimide with analogue azobenzene dyes on natural and synthetic polymers. Arabian Journal of Chemistry. 2014. |
| [4] | Aktan E, Babur B, Seferoglu Z, Hokelek T and Sahin E, J. Mol. Stru., (2) 2011, 113-120. |
| [5] | Rau H, 1990. Rabek, JF., ed. Photochemistry and Photophysics 2. Boca Raton, FL: CRC Press. 2011, 119–141. |
| [6] | Yager KG and Barrett, CJ, "Chapter 17 - Azobenzene Polymers as Photomechanical and Multifunctional Smart Materials". In Shahinpoor, M, Schneider HJ, Intelligent Materials. Cambridge: Royal Society of Chemistry. 2008, 426–427. |
| [7] | Hartley GS, The cis-form of azobenzene. Nature. 140 1937, 281. |
| [8] | Torres-Zúñiga V, Morales-Saavedra OG, Rivera E, Castañeda-Guzmán R, Bañuelos, JG and Ortega-Martínez R, "Preparation and photophysical properties of monomeric liquid-crystalline azo-dyes embedded in bulk and film SiO2-sonogel glasses". Journal of Sol-Gel Science and Technology 56 (1) 2010, 7–18. |
| [9] | Faustino H, El-Shistawy RM, Reis LV, Santos PF and Almeida P, Tetrahedron Letters. (49) 2008, 6907-6909. |
| [10] | Cui Y, Qian G, Gao, J, Chen L, Wang Z and Wang M, Preparation and Nonlinear Optical Properties of Inorganic-Organic Hybrid films with Various Substituents on Chromophores. J. Phys. Chem. B. (109) 2005, 23295-23299. |
| [11] | Lee YO, Pradhan T, No K and Kim, JS, N, N-Dimethylaniline and 1-(trifluoromethyl) benzene-functionalized tetrakis (ethynyl) pyrenes: synthesis, photophysical, electrochemical and computational studies. Tetrahedron. (68) 2012, 1704-1711. |
| [12] | Islam MM, Bhiuyan MDH, Bredow T and Try AC, Theoretical investigation of the nonlinear optical properties of substituted anilines and N, N-Dimethylanilines. Comput. Theor. Chem. (967) 2011, 165-170. |
| [13] | Grozema FC, Telesca R, Jonkman HT, Siebbeles LDA and Snijders JG, Excited state polarizabilities of conjugated molecules calculated using time dependent density functional theory. J. Chem. Phys. (115) 2001, 10014-10021. |
| [14] | Targema M, Obi-Egbedi NO and Adeoye MD, Molecular structure and solvent effects on the dipole moments and polarizabilities of some aniline derivatives. Computational and Theoretical Chemistry. (1012) 2013, 47-53. |
| [15] | Adejoro IA, Ibeji CU and Aigbe AE, Theoretical study on substituent effect on the properties of Benzofused thieno [3,2-b] furan and its isomeric form. Nature and Science. (11) 2013, 75-82. |
| [16] | Yitzchaik S and Marks T, J. Acc. Chem. Res. (29)1996, 197. |
| [17] | Levy D, Esquivias. Adv. Mater. (7) 1995, 120. |
| [18] | Sisido M, Ishikawa Y, Harada M and Ito K, Macromolecules. (24)1991), 3999. |
| [19] | Jung C, Takehisa C, Sakata Y and Kaneda T, Chem Lett. 1996, 147. |
| [20] | Yamamura H, Kawai H, Yotsuya T, Higuchi T, Butsugan Y, Araki S, Kawai M and Fujita K. Chem. Lett. 1996, 799. |
| [21] | Liu X, Bruce D and Manners I, Chem. Commun.1997, 289. |
| [22] | Junge, D and McGrath D, Chem. Commun.1997, 857. |
| [23] | Omar MA, Elementary Solid State Physics, 1974, Chapt. 8, Addison Wesley, London. |
| [24] | Kavitha E, Sundaraganesan N and Sebastian S, Molecular structure, vibrational soectroscopy and HOMO, LUMO studies of 4-nitroaniline by density functional theory method. Indian Journal of Pure and Applied Physics. (48) 2010, 20-30. |
| [25] | Sridevi C, Shanthi G and Velraj G, Structural, vibrational, electronic, NMR and reactivity analyses of 2-amino-4H-chromene-3-carbonitrile (ACC) by ab initio HF and DFT calculations, Spectrochem. Acta. Part A (89) 2012, 46-54. |
| [26] | Milman V, Refson K, Clark SJ, Pickard CJ, Yates KR, Gao SP, Hasnip PJ, Probert MIJ, Perlov A and Segall MD, Electron and Vibrational Spectroscopies using DFT, plane waves and pseudopotentials: CASTEP implementation. J. Mol. Struc. (THEOCHEM). (954) 2010, 22-35. |
| [27] | (a) Jursic BS and Can J, Theoretical study on Benzofused thieno [3, 2-b] Furan bromination mechanism. Chemistry. (74) 1996,114. (b) Jursic BS and Zdravskovski Z, Theoretical study of benzofused [3, 2-b] furans in the reaction with electrophiles. Int. J. Quantum Chemistry. (54) 1994, 161. |
| [28] | Nathaniel R, Mineva T, Nikolova R and Bojilova A, Density Functional Study of the interaction of (3-bromoacetyl) coumarin with phosphate. Int. J. Quantum Chemistry. (106) 2006, 1357. |
| [29] | Hohenberg P and Kohn W, Inhomogeneous electron gas, Phys. Rev. 136B1964, 864–871. |
| [30] | Kohn W and Sham LJ, Phys. Rev. 140A 1965, 1133. |
| [31] | Becke AD, Density Functional Thermochemistry. III. The role of exact exchange. J. Chem. Phys. (98) 1993 5648-5652. |
| [32] | Hotta S, Kimura H, Lee SAT and Tamaki T, J. Heterocycl. Chem. (37) 2000, 281. |
| [33] | Dewar M, Thiel W, Semi Empirical Quantum Chemistry. J. Am. Chem. Soc. (99)1977, 4499. |
| [34] | McMurryF, Chemistry fourth edition. Pearson Education. New Jersey. 2002. |
| [35] | Shao Y, Molnar LF, Jung Y, Kussmann J, Ochsenfeld C, Brown ST, Gilbert ATB, Slipchenko LV, Levchenko SV, O’Neill DP, DiStasio Jr RA, Lochan RC, Wang T, Beran GJO, Besley NA, Herbert JM, Lin CY, Van Voorhis T, Chien SH, Sodt A, Steele RP, Rassolov VA, Maslen PE, Korambath PP, Adamson RD, Austin B, Baker J, Byrd EFC, Dachsel H, Doerksen RJ, Dreuw A, Dunietz BD, Dutoi AD, Furlani TR, Gwaltney SR, Heyden A, Hirata S, Hsu CP, Kedziora G, Khalliulin RZ, Klunzinger P, Lee AM, Lee MS, Liang WZ, Lotan I, Nair N, Peters B, Proynov EI, Pieniazek PA, Rhee YM, Ritchie J, Rosta E, Sherrill CD, Simmonett, AC, Subotnik JE, Woodcock III HL, Zhang W, Bell AT, Chakraborty AK, Chipman DM, Keil FJ, Warshel A, Hehre WJ, Schaefer HF, Kong J, Krylov AI, Gill PMW, Head-Gordon M, Deepmer BJ, Driessen AJ, Hehre TS, Johnson JA, Pietro WJ, Yu J, SPARTAN '10, build 1.01 Wavefunction Inc. Irvine CA, 2011. |
| [36] | Gece G, The use of quantum chemical methods in corrosion inhibitor studies. Corros. Sci. (50) 2008, 2981-2992. |
| [37] | Atkins PW and Friedman RS, Molecular Quantum Mechanics, Fourth edition. University Press, New York. 2004. |
| [38] | Ramachandran RE, Deepa G and Namboori K, Computational Chemistry and Molecular Modelling: Principles and Applications. Springer-Verlag. Berlin Heidelberg. 2008. |
| [39] | Zhou L, Lee FX, Wilcox W and Christensen J, Magnetic polarizability of hadrons from lattice. QCD. European Organization for Nuclear Research. (CERN). 2002. |
| [40] | Introduction to Electrodynamics (3rd Edition), Griffiths DJ, Pearson Education, Dorling Kindersley, 2007. |
| [41] | Koopmans T, “Uber die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines atoms”. Physica (Elsevier). 1 (1-6): 1990, 104-113. |
| [42] | Zhou Z and Parr RG, Activation hardness: new index for describing the orientation of electrophilic aromatic substitution, J. Am. Chem. Soc. (112) 1990, 5720–5724. |
| [43] | Lewis DFV, Ioannides C and Parke DV, Interaction of a series of nitriles with the alcohol-inducible isoform of P450: Computer analysis of structure–activity relationships, Xenobiotica 24: 1994, 401–408. |
| [44] | Kikuchi O, Systematic QSAR procedures with quantum chemical descriptors, Quant. Struct.-Act. Relat. (6) 1987, 179–184. |
| [45] | Motinger RG, Physical Chemistry, Third Ed., Elsevier Inc., USA, 2008. |
| [46] | Meyer WH, Kiess H, Binggeli B, Meier E and Harbeke G, Polymer for use in information storage. Synth. Met. (10) 1985, 225-259. |
| [47] | Shikarawa H, Louis EJ, MacDiarmid AG, Chiang CK and Heeger AJ, Chem. Comm. 1977, 578. |
| [48] | Mingxin D, Amirhossein B, Subhas S, Andrew AB and Andrew GW. Red-Shifting Azobenzene Photoswitches for In Vivo use. Acct. Chem Res. 48 (10): 2015, 2662-2670. |
| [49] | Ridhima C, Nandita M and Sudhir K. Interaction of anthranilic acid with silver nanoparticles: A Raman, surface-enhanced Raman scattering and density functional theoretical study. Journal of Molecular Structure. 1076. 2014, 35-41. |
APA Style
Isaiah Ajibade Adejoro, Oluwatoba Emmanuel Oyeneyin, Babatunde Temitope Ogunyemi. (2015). Computational Investigation on Substituent and Solvent Effects on the Electronic, Geometric and Spectroscopic Properties of Azobenzene and Some Substituted Derivatives. International Journal of Computational and Theoretical Chemistry, 3(6), 50-57. https://doi.org/10.11648/j.ijctc.20150306.12
ACS Style
Isaiah Ajibade Adejoro; Oluwatoba Emmanuel Oyeneyin; Babatunde Temitope Ogunyemi. Computational Investigation on Substituent and Solvent Effects on the Electronic, Geometric and Spectroscopic Properties of Azobenzene and Some Substituted Derivatives. Int. J. Comput. Theor. Chem. 2015, 3(6), 50-57. doi: 10.11648/j.ijctc.20150306.12
AMA Style
Isaiah Ajibade Adejoro, Oluwatoba Emmanuel Oyeneyin, Babatunde Temitope Ogunyemi. Computational Investigation on Substituent and Solvent Effects on the Electronic, Geometric and Spectroscopic Properties of Azobenzene and Some Substituted Derivatives. Int J Comput Theor Chem. 2015;3(6):50-57. doi: 10.11648/j.ijctc.20150306.12
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Download@article{10.11648/j.ijctc.20150306.12,
author = {Isaiah Ajibade Adejoro and Oluwatoba Emmanuel Oyeneyin and Babatunde Temitope Ogunyemi},
title = {Computational Investigation on Substituent and Solvent Effects on the Electronic, Geometric and Spectroscopic Properties of Azobenzene and Some Substituted Derivatives},
journal = {International Journal of Computational and Theoretical Chemistry},
volume = {3},
number = {6},
pages = {50-57},
doi = {10.11648/j.ijctc.20150306.12},
url = {https://doi.org/10.11648/j.ijctc.20150306.12},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20150306.12},
abstract = {Computational investigation on the ground state properties of trans-azobenzene and four kinds of hydroxy-ended azobenzene-type chromophores containing different substituent groups as electron donor and acceptor in different solvent media was carried out. The effects ofsubstituents –I2, -OH- and -CH3, -NH2, and –Cl2 on the electronic properties like the EHOMO, ELUMO, band gap, dipole moments, global hardness, electrophilicity indices were studied using the Ab initio restricted DFT self-consistent field method with the Becke Three Lee Yang Parr (B3LYP)/6-31G* method in vacuum, water, diethylether, ethanol and acetone. The results showed that these properties were altered upon substitution with different groups. The azobenzene gave a slight difference in its band gap in different solvent changing from (3.95 eV) in vacuum to the lowest (3.87 eV) in acetone but changes drastically as we introduce different substituents. It was also found that the dipole moment (μ), polarizability (α), absorption wavelength (λab) gave slight change in different solvents but rapidly increased as the band gap reduces, invoking their reactivities. They are also red-shifted as different substituents are added. Of all the studied molecules, compound H gave the lowest band gap of 0.46 eV, the highest dipole moment (875.02 D), the highest polarizability (64.97C.m2V-1) and it is the most red-shifted (401.13 nm). Molecule H therefore, has the lowest band gap, highest polarizability and dipole moment. It also has the highest molecular size and the highest planarity. This means that the molecule is the most reactive, most polarizable, highest electro-optic response and it is the softest.},
year = {2015}
}
TY - JOUR T1 - Computational Investigation on Substituent and Solvent Effects on the Electronic, Geometric and Spectroscopic Properties of Azobenzene and Some Substituted Derivatives AU - Isaiah Ajibade Adejoro AU - Oluwatoba Emmanuel Oyeneyin AU - Babatunde Temitope Ogunyemi Y1 - 2015/12/16 PY - 2015 N1 - https://doi.org/10.11648/j.ijctc.20150306.12 DO - 10.11648/j.ijctc.20150306.12 T2 - International Journal of Computational and Theoretical Chemistry JF - International Journal of Computational and Theoretical Chemistry JO - International Journal of Computational and Theoretical Chemistry SP - 50 EP - 57 PB - Science Publishing Group SN - 2376-7308 UR - https://doi.org/10.11648/j.ijctc.20150306.12 AB - Computational investigation on the ground state properties of trans-azobenzene and four kinds of hydroxy-ended azobenzene-type chromophores containing different substituent groups as electron donor and acceptor in different solvent media was carried out. The effects ofsubstituents –I2, -OH- and -CH3, -NH2, and –Cl2 on the electronic properties like the EHOMO, ELUMO, band gap, dipole moments, global hardness, electrophilicity indices were studied using the Ab initio restricted DFT self-consistent field method with the Becke Three Lee Yang Parr (B3LYP)/6-31G* method in vacuum, water, diethylether, ethanol and acetone. The results showed that these properties were altered upon substitution with different groups. The azobenzene gave a slight difference in its band gap in different solvent changing from (3.95 eV) in vacuum to the lowest (3.87 eV) in acetone but changes drastically as we introduce different substituents. It was also found that the dipole moment (μ), polarizability (α), absorption wavelength (λab) gave slight change in different solvents but rapidly increased as the band gap reduces, invoking their reactivities. They are also red-shifted as different substituents are added. Of all the studied molecules, compound H gave the lowest band gap of 0.46 eV, the highest dipole moment (875.02 D), the highest polarizability (64.97C.m2V-1) and it is the most red-shifted (401.13 nm). Molecule H therefore, has the lowest band gap, highest polarizability and dipole moment. It also has the highest molecular size and the highest planarity. This means that the molecule is the most reactive, most polarizable, highest electro-optic response and it is the softest. VL - 3 IS - 6 ER -
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