Investigating the Effect of Tuning the Metal Center in Complexes for Nonlinear Optical Application
Keywords:Density functional theory, Nonlinear optic property, Nickel complex, Zinc complex
In this study, the new transition metal complexes, ML with M = Zn (II), Ni (II), and Pd (II) based on the N,N'-Bis[O-(diphenylphosphino)benzylidene)ethylenediamine ligand were successfully synthesized with a percentage yield of between 33 – 68%. As a result of fourier transform infrared spectroscopy (FTIR), UV-vis spectroscopy (UV-vis), and 1H nuclear magnetic resonance (proton NMR) was used to design and completely describe the metal complexes properties. Moreover, for computational study, the Gaussian16 software installed in the high-performance computer (HPC) is used for NLO calculation. The method used to perform this study is Density Functional Theory (DFT) method. 6-31G(d,p) basis set is used with LANL2DZ for zinc, nickel, and palladium along with the keyword ‘GEN’. The molecular structure has been optimized and checked both bond length and bond angle before starting to run the calculation. Thus, NLO calculation had been performed. The dipole moment and the HOMO-LUMO energy gap were employed to verify the first hyperpolarizability, βtot, which can be utilized as an indication of second nonlinear optical characteristics. Transition metal-based complexes produce impressive results because they provide additional flexibility by offering charge transfer (CT) transitions between the metal and the ligands, resulting in a higher NLO response. Due to the charge transfer excitations, it was discovered that the nickel complex with 2.87 D had the largest NLO response (117215.66 x 10-30 esu), particularly in comparison with the zinc complex (2329.72 x 10-30 esu) and palladium complex (191.07 x 10-30 esu) with 6.52 D and 4.04 D values, respectively.
Baldwin, G. C. (2012). An introduction to nonlinear optics. Springer Science & Business Media.
Boyd, R. W., & Prato, D. (2008). Nonlinear Optics. USA: Elsevier Science.
Suresh, S., Ramanand, A., Jayaraman, D., & Mani, P. (2012). Review on theoretical aspect of nonlinear optics. Reviews on Advanced Materials Science, 30(2), 175-183.
Butet, J., Brevet, P.-F., & Martin, O. J. F. (2015). optical second harmonic generation in plasmonic nanostructures: From fundamental principles to advanced applications. ACS Nano, 9(11), 10545-105.
Green, K. A., Cifuentes, M. P., Samoc, M., & Humphrey, M. G. (2011). Metal alkynyl complexes as switchable NLO systems. Coordination Chemistry Reviews, 255(21), 2530-2541.
Bibi, T., Jadoon, T., Muhammad, S., & Ayub, K. (2021). Second order NLO properties and two-state switching effects of transition metal redox complexes of iron and cobalt: A DFT study. Journal of Molecular Graphics and Modelling, 107, 107975.
Anitha, C., Sumathi, S., Tharmaraj, P., & Sheela, C. (2012). Synthesis, characterization, and biological activity of some transition metal complexes derived from novel hydrazone azo schiff base ligand. International Journal of Inorganic Chemistry, 2011.
Chavan, S. S., Pawal, S. B., Lolage, S. R., & Garadkar, K. M. (2017). Synthesis, spectroscopic characterization, luminescence and NLO properties of heterometallic M(II)-Ru(II) (M=Ni and Zn) hybrid complexes composed of coordination and organometallic sites. Journal of Organometallic Chemistry, 853, 18-26.
Chavan, S. S., & Bharate, B. G. (2013). Heterobimetallic M(II)/Ru(II) (M=Ni, Zn) complexes containing coordination and organometallic sites: Synthesis, characterization, luminescence and NLO properties. Inorganica Chimica Acta, 394, 598-604.
Lind, P. (2007). Organic and organometallic compounds for nonlinear absorption of light. Kemi.
Comba, P., Hambley, T. W., & Martin, B. (2009). Molecular modeling of inorganic compounds. John Wiley & Sons.
Errol, G. L. (2011). Computational Chemistry: Introduction to the theory and applications of molecular and quantum mechanics. Springer, New York. 43, 44-45.
Perdew, J. P., & Yue, W. (1986). Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation. Physical review B, 33(12), 8800.
Siegbahn, P. E. (2006). The performance of hybrid DFT for mechanisms involving transition metal complexes in enzymes. JBIC Journal of Biological Inorganic Chemistry, 11(6), 695-701.
Lakshmi, C. S. N., Balachandran, S., Arul, D. D., Ronaldo, A. A., & Hubert, J. I. (2019). DFT analysis on spectral and NLO properties of (2E)-3-[4- (dimethylamino) phenyl]-1-(naphthalen-2-yl) prop-2-en-1-one; a d-π-A chalcone derivative and its docking studies as a potent hepatoprotective agent.
Muscat, J., Swamy, V., & Harrison, N. M. (2002). First-principles calculations of the phase stability of TiO2. Physical Review B, 65(22), 224112.
Foresman, J., & Frisch, A. (2015). Exploring Chemistry with Electronic Structure Methods. 3rd edn., Wallingford, CT USA, Gaussian. In: Inc.
Mohamed, M. A., Mohd Hir, Z. A., Wan Mokthar, W. N. A., & Osman, N. S. (2020). 6 - Features of metal oxide colloidal nanocrystal characterization. In S. Thomas, A. Tresa Sunny, & P. Velayudhan (Eds.). Colloidal Metal Oxide Nanoparticles (pp. 83-122): Elsevier.
Karakas, A., Dag, T., Taser, M., Fillaut, J., Migalska-Zalas, A., & Sahraoui, B. (2013). Second order hyperpolarizability and susceptibility calculations of a series of ruthenium complexes. Paper presented at the 2013 15th International. Conference on Transparent Optical Networks (ICTON).
Baseia, B., Osório, F. A., Lima, L. F., & Valverde, C. (2017). Effects of changing substituents on the non-linear optical properties of two coumarin derivatives. Crystals, 7(6), 158.
Khalid, M., Lodhi, H. M., Khan, M. U., & Imran, M. (2021). Structural parameter-modulated nonlinear optical amplitude of acceptor–π–D–π–donor-configured pyrene derivatives: A DFT approach. RSC Advances, 11(23), 14237-14250.
Cole, J. M., & Ashcroft, C. M. (2018). Generic classification scheme for second-order dipolar nonlinear optical organometallic complexes that exhibit second harmonic generation. The Journal of Physical Chemistry A, 123(3), 702-714.
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