Nonlinear optical response of D-π-A chromophores based on benzoxazin: quantum modification of π‑spacer

Abstract: In this research article, four chromophores based on benzoxazine as the electron donor and tricyanovinyl dihydrofuran (TCF) as the electron acceptor have been designed to investigate the nonlinear optical (NLO) response. The geometric and electronic structures, absorption spectra, NBO analysis, and nonlinear optical response have been calculated by employing density functional theory (DFT) at PBEPBE/6-31G (d,p). The new design of chromophores has been proposed by the structural modification of π-spacers/conjugated systems. The DFT and TD−DFT computations at CAM−B3LYP/6−31G (d,p) have been performed to shed light on the influences of structural modification on the NLO properties. The absorption wavelength in different organic solvents, polarizability (α), and hyperpolarizability (β) are all determined. A strong NLO response indicates that this family of organic compounds with a D-π-A structure exhibits large first hyperpolarizability βtot values, these values are much greater than ones of urea. This theoretical model may be used to design other chromophores for usage in electro-optics.

How to cite this paper

 Azaid, A., Abram, T., Kacimi, R., Raftani, M., Khaddam, Y., Nebbach, D., Sbai, A., Lakhlifi, T & Bouachrine, M. (2022). Nonlinear optical response of D-π-A chromophores based on benzoxazin: quantum modification of π‑spacer.Current Chemistry Letters, 11(3), 331-340.

Refrences

1 Costes J. P., Lamère J. F., Lepetit C., Lacroix P. G., Dahan F., & Nakatani K. (2005) Synthesis, Crystal Structures, and Nonlinear Optical (NLO) Properties of New Schiff-Base Nickel(II) Complexes. Toward a New Type of Molecular Switch. Inorg Chem., 44 (6) 1973-1982.
2 Santo D. B., & Fragalà I. (2000) Synthesis and second-order nonlinear optical properties of bis (salicylaldiminato) M (II) metalloorganic materials. Synthetic Metals., 115 (1-3) 191-196.
3 Lacroix P. G. (2001) second-Order Optical Nonlinearities in Coordination Chemistry: The Case of Bis (salicylaldiminato) metal Schiff Base Complexes. Eur J Inorg Chem., 2001 (2) 339-348.
4 Williams D. J. (1984) Organic Polymeric and Non-Polymeric Materials with Large Optical Nonlinearities. Angew Chem Int Ed Engl., 23 (9) 690 -703.
5 Janjua M. R. S. A. (2017) Nonlinear optical response of a series of small molecules: quantum modification of π-spacer and acceptor. J Iran Cheme SOC., 14 (9) 2041-2054.
6 Zhong R. L., Xu H. L., Li Z. R., & Su ZM. (2015) Role of Excess Electrons in Nonlinear Optical Response. J Phys Chem Lett., 6 (4) 612-619.
7 Muhammad S., Xu H. L., Zhong R. L., Su Z. M., Al-Sehemi A. G., & Irfan A. (2013) Quantum chemical design of nonlinear optical materials by sp2-hybridized carbon nanomaterials: issues and opportunities. J Mater Chem C., 1 (35) 5439.
8 Garza A. J., Osman O. I., Wazzan N. A., Khan S. B., Asiri A. M., and Scuseria G. E. (2014) A computational study of the nonlinear optical properties of carbazole derivatives: theory refines experiment. Theor Chem Acc., 133 (4) 1458.
9 Janjua M. R. S. A., Amin M., Ali M., Bashir B., Khan M. U., Iqbal M. A., Guan W., Yan L., and Su Z. M (2012) A DFT Study on The Two-Dimensional Second-Order Nonlinear Optical (NLO) Response of Terpyridine-Substituted Hexamolybdates: Physical Insight on 2D Inorganic-Organic Hybrid Functional Materials. Eur J Inorg Chem., 2012 (4) 705-711.
10 Dalton L. (2002) Nonlinear Optical Polymeric Materials: From Chromophore Design to Commercial Applications. Advances in Polymer Science., 158 1-86.
11 Dulcic A., Flytzanis C., Tang C. L., Pépin D., Fétizon M., & Hoppilliard Y. (1981) Length dependence of the second‐order optical nonlinearity in conjugated hydrocarbons. The Journal of Chemical Physics., 74 (3) 1559 -1563.
12 Zyss J., & Ledoux I. (1994) Nonlinear optics in multipolar media: theory and experiments. Chem Rev., 94 (1) 77-105.
13 Entwistle C. D., Collings J. C., Steffen A., Palsson L. O., Beeby A., Jove D. A., Burke J. M., Batsanov A S., Howard J. A. K., Mosely J. A., Poon S. Y., Wo W. Y., Ibersiene F., Fathallah S., Boucekkine A., Halet J. F. O., & Marder T. B. (2009) Syntheses, structures, two-photon absorption cross-sections and computed second hyperpolarisabilities of quadrupolar A–π–A systems containing E-dimesitylborylethenyl acceptors. J Mater Chem., 19 (40) 7532-7544.
14 Wang H., Zhang M., Yang Y., Liu F., Hu C., Xiao H., Qiu L., Liu X., Liu J., & Zhen Z. (2016) Synthesis and characterization of one novel second-order nonlinear optical chromophore based on new benzoxazin donor. Materials Letters., 164 644 - 646.
15 Becke A. D. (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A., 38 (6) 3098-3100.
16 Lee C., Yang W., & Parr R. G. (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B., 37 (2) 785-789.
17 Perdew J. P., Burke K., & Ernzerhof M. (1996) Generalized Gradient Approximation Made Simple. Phys Rev Lett., 77 (18) 3865-3868.
18 Govindarajan M., Ganesan K., Periandy S., and Mohan S. (2010) DFT (LSDA, B3LYP and B3PW91) comparative vibrational spectroscopic analysis of -acetonaphthone. Inorganica Chimica Acta., 486 162–171.
19 Adamo C., & Barone V. (1998) Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models. The Journal of Chemical Physics., 108 (2) 664-675.
20 Stratmann R. E., Scuseria G. E., & Frisch M J. (1998) An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules. The Journal of Chemical Physics., 109 (19) 8218-8224.
21 Casida M. E., Jamorski C., Casida K. C., & Salahub D. R. (1998) Molecular excitation energies to high-lying bound states from time-dependent local density approximation ionization threshold. The Journal of Chemical Physics., 108 (11) 4439-44
22 Frisch C. J., Trucks G. W., Schlegel H. B., Scuseria G. E , Robb M. A., et al, (2009) Gaussian 09, Revision A.02.
23 Kumer A., Chakma, U., Matin M. M., Akash S., Chando A., & Howlader D. (2021) The computational screening of inhibitor for black fungus and white fungus by D-glucofuranose derivatives using in silico and SAR study. Org. Commun., 14 (4) 305-322.
24 Islam N., Islam M. D., Rahman M. R., & Matin M. M. (2021) Octyl 6-O-hexanoyl-β-D-glucopyranosides: Synthesis, PASS, antibacterial, in silico ADMET, and DFT studies. Curr. Chem. Lett., 10 (4) 413-426.
25 Hanee U., Rahman M. R., & Matin M. M. (2021) Synthesis, PASS, in silico ADMET, and thermodynamic studies of some galactopyranoside esters. Phys. Chem. Res., 9 (4) 591-603.
26 Foster J. P., and Weinhold F. (1980) Natural hybrid orbitals. J Am Chem Soc., 102 (24) 7211-7218.
27 Guillaumont D., & Nakamura S. (2000) Calculation of the absorption wavelength of dyes using time-dependent density-functional theory (TD-DFT). Dyes and Pigments., 46( 2) 85-92.
28 Yanai T., Tew D. P., & Handy N. C. (2004) A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP). Chemical Physics Letters., 393(1-3) 51-57.
29 Lin C., & Wu K. (2000) Theoretical studies on the nonlinear optical susceptibilities of 3-methoxy-4-hydroxy-benzaldehyde crystal. Chemical Physics Letters., 321 (1-2) 83-88.
30 Karamanis P., Pouchan C., & Maroulis G. (2008) Structure, stability, dipole polarizability and differential polarizability in small gallium arsenide clusters from all-electron ab initio and density-functional-theory calculations. Phys Rev A., 77 (1) 013201.
31 Ghanavatkar C. W., Mishra V. R., & Sekar N. (2021) Review of NLO phoric azo dyes – Developments in hyperpolarizabilities in last two decades. Dyes and Pigments., 191 109367.
32 Kacimi R., Bourass M., Toupance T., Wazzan N., Chemek M., El Alamy A,. Bejjit L., Alimi K., & Bouachrine M. (2020) Computational design of new organic (D–π–A) dyes based on benzothiadiazole for photovoltaic applications, especially dye-sensitized solar cells. Res Chem Intermed., 46 (6) 3247-3262.
33 Etabti H., Fitri A., Benjelloun A. T., Hachi M., Benzakour M., & Mcharfi M. (2021) Benzocarbazole-based D–Di–π–A dyes for DSSCs: DFT/TD-DFT study of influence of auxiliary donors on the performance of free dye and dye–TiO2 interface. Res Chem Intermed., 47 (10) 4257-4280.
34 Rajan V. K., & Muraleedharan K. (2017) A computational investigation on the structure, global parameters and antioxidant capacity of a polyphenol, Gallic acid. Food Chemistry., 220 93-99.
35 Daolio A., Pizzi A., Calabrese M., Terraneo G., Bordignon S., Frontera A., & Resnati, V. (2021) Molecular Electrostatic Potential and Noncovalent Interactions in Derivatives of Group 8 Elements. Zitierweise: Angew. Chem. Int. Ed., 60 (133) 20723 – 20727.
36 Wang H, Wang X, Wang H, Wang L, & Liu A. (2007) DFT study of new bipyrazole derivatives and their potential activity as corrosion inhibitor. J Mol Model., 13 147–153.
37 Raftani M., Abram T., Loued W., Kacimi R., Azaid A., Alimi K., Bennani M. N., & Bouachrinea M. (2021) The optoelectronic properties of π-conjugated organic molecules based on terphenyl and pyrrole for BHJ solar cells: DFT / TD-DFT theoretical study. Current Chemistry Letters., 10 (4) 489-502.
38 Islam N., & Ghosh D. C. (2012) On the Electrophilic Character of Molecules Through Its Relation with Electronegativity and Chemical Hardness. International Journal of Molecular Sciences., 13 2160-2175.
39 Parr R. G., & Pearson R. G. (1983) Absolute hardness: companion parameter to absolute electronegativity. J Am Chem Soc., 105 (26) 7512-7516.
40 Parr R. G., Donnelly R. A., Levy M., & Palke W. E. (1978) Electronegativity: The density functional view point. The Journal of Chemical Physics., 68 (8) 3801-3807.
41 Aziz S. G., Elroby S. A. K., Hilal R. H., & Osman O. I. (2014) Theoretical and computational studies of conformation, natural bond orbital and nonlinear optical properties of cis-N-phenylbenzohydroxamic acid. Computational and Theoretical Chemistry., 1028 65-71.
42 Peng Z., & Yu L. (1994) Second-Order Nonlinear Optical Polyimide with High-Temperature Stability. Macromolecules., 27 (9) 2638-2640.
43 Tsutsumi N., Morishima M., & Sakai W. (1998) Nonlinear Optical (NLO) Polymers. 3. NLO Polyimide with Dipole Moments Aligned Transverse to the Imide Linkage. Macromolecules., 31 (22) 7764-7769.
44 Hussain A., Khan M. U., Ibrahim M., Khalid M., Ali A., Hussain S., Saleem M., Ahmad N., Muhammad S., Al-Sehemi A G., & Sultan A. (2020) Structural parameters, electronic, linear and nonlinear optical exploration of thiopyrimidine derivatives: A comparison between DFT/TDDFT and experimental study. Journal of Molecular Structure., 1201 127-183.
45 Jawaria R., Hussain M., Khalid M., Khan U. M., Tahir N. M., Naseer M. M., Braga C. A. A., & Shafiq Z. (2019) Synthesis, crystal structure analysis, spectral characterization and nonlinear optical exploration of potent thiosemicarbazones based compounds: A DFT refine experimental study. Inorganica Chimica Acta., 486 162-171.
46 Zaitri L. K., & Mekelleche S. M. (2021) DFT and TD-DFT Study on Quadratic NLO Response and Optoelectronic Activity in Novel Y-Shaped Imidazole-Based Push-Pull Chromophores. In Review., 136 (27) 1-14.
47 Khalid M., Khan M. U., Shafiq I., Hussain R., Mahmood K., Hussain A., Jawaria R., Hussain A,. Imran M., Assiri M. A., Ali A., Rehman M. F. U., Sun K., & Li Y. (2021) NLO potential exploration for D–π–A heterocyclic organic compounds by incorporation of various π-linkers and acceptor units. Arabian Journal of Chemistry., 14 (8) 1878-5352.