Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 Nov 16;13(1):20104.
doi: 10.1038/s41598-023-44327-9.

Promising impact of push-pull configuration into designed octacyclic naphthalene-based organic scaffolds for nonlinear optical amplitudes: a quantum chemical approach

Muhammad Khalid  1   2 , Iqra Shafiq  1   2 , Muhammad Adnan Asghar  3 , Ataualpa Albert Carmo Braga  4 , Saad M Alshehri  5 , Muhammad Haroon  6 , Muhammed Lamin Sanyang  7
Affiliations

Promising impact of push-pull configuration into designed octacyclic naphthalene-based organic scaffolds for nonlinear optical amplitudes: a quantum chemical approach

Muhammad Khalid et al. Sci Rep. .

Abstract

In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1-D9) with D-π-A configuration from PCMR. DFT analysis at M06/6-311G (d,p) level was accomplished to explore the photonic behavior of PCMD1-D9 compounds. Various kind of analysis like; UV-Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1 with the least band gap of 2.048 eV in PCMD8 among all the compounds. The UV-Visible spectrum of the entitled chromophores manifested high values of λmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization (34.31 kcal/mol) for PCMD8 chromophore. The highest linear polarizability (<α>) and dipole moment (µtot) values were exhibited by PCMD5 at 2.712 × 10-22. and 1.995 × 10-17 esu, respectively. PCMD8 push-pull configured molecular entity exhibited highest first hyper-polarizability (βtot) at 4.747 × 10-27 esu and second hyper-polarizability at 6.867 × 10-32 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
Synthesized chromophore NITT-BF modification into reference PCMR by substitution of methyl group. These structures are drawn with the help of ChemDraw software (https://chemistrydocs.com/chemdraw-pro-8-0/ ).
Figure 2
Figure 2
Schematic demonstration of D–π–A configured PCMR and PCMD1–D9 chromophores with variant acceptors. This scheme is drawn with the help of ChemDraw software (https://chemistrydocs.com/chemdraw-pro-8-0/).
Figure 3
Figure 3
The excited and ground states (HOMO–LUMO) ΔE values for PCMR and PCMD1–D9 at M06/6-311G(d,p) and output files were calculated through Gaussian 09 version D.01.
Figure 4
Figure 4
Density of states diagrams of PCMR and PCMD1–D9 at M06/6-311G(d,p) level. Figures were drawn by utilizing PyMOlyze 1.1 version and output files were calculated through Gaussian 09 version D.01.
Figure 5
Figure 5
PCMR and PCMD1–D9 computed ultraviolet–visible spectrum in gas medium illustrated by Origin Pro 8.5.
Figure 6
Figure 6
Pictorial representation of TDMs heat maps for PCMR and PCMD1–D9 illustrated using Multiwfn 3.7 program (http://sobereva.com/multiwfn/).
Figure 6
Figure 6
Pictorial representation of TDMs heat maps for PCMR and PCMD1–D9 illustrated using Multiwfn 3.7 program (http://sobereva.com/multiwfn/).
See this image and copyright information in PMC

References

    1. Brown F, Parks RE, Sleeper AM. Nonlinear optical reflection from a metallic boundary. Phys. Rev. Lett. 1965;14:1029. doi: 10.1103/PhysRevLett.14.1029. - DOI
    1. Castro MCR, Belsley M, Raposo MMM. Push–pull second harmonic generation chromophores bearing pyrrole and thiazole heterocycles functionalized with several acceptor moieties: Syntheses and characterization. Dyes Pigm. 2016;128:89–95. doi: 10.1016/j.dyepig.2016.01.015. - DOI
    1. Anis M, Shaikh RN, Shirsat MD, Hussaini SS. Investigation of optical and electrical properties of L-cystein doped zinc thiourea chloride (ZTC) crystal for nonlinear optical (NLO) applications. Opt. Laser Technol. 2014;60:124–129. doi: 10.1016/j.optlastec.2014.01.011. - DOI
    1. Bano R, et al. Diamondoid as potential nonlinear optical material by superalkali doping: A first principles study. Diam. Relat. Mater. 2023;135:109826. doi: 10.1016/j.diamond.2023.109826. - DOI
    1. Mahmood A, Abdullah MI, Nazar MF. Quantum chemical designing of novel organic non-linear optical compounds. Bull. Korean Chem. Soc. 2014;35:1391–1396. doi: 10.5012/bkcs.2014.35.5.1391. - DOI