Role of donors in triggering second order non-linear optical properties of non-fullerene FCO-2FR1 based derivatives: A theoretical perspective

Muhammad Khalid; Mashal Khan; Iqra Shafiq; Khalid Mahmood; Muhammad Nadeem Akhtar; Javed Iqbal; Mohammad Khalid Al-Sadoon; Wajid Zaman; Ataualpa Albert Carmo Braga

doi:10.1016/j.heliyon.2023.e13033

Role of donors in triggering second order non-linear optical properties of non-fullerene FCO-2FR1 based derivatives: A theoretical perspective

Heliyon. 2023 Jan 17;9(2):e13033. doi: 10.1016/j.heliyon.2023.e13033. eCollection 2023 Feb.

Authors

Muhammad Khalid^{1

2}, Mashal Khan^{1

2}, Iqra Shafiq^{1

2}, Khalid Mahmood³, Muhammad Nadeem Akhtar⁴, Javed Iqbal⁵, Mohammad Khalid Al-Sadoon⁶, Wajid Zaman⁷, Ataualpa Albert Carmo Braga⁸

Affiliations

¹ Institute of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan.
² Centre for Theoretical and Computational Research, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan.
³ Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, 60800, Pakistan.
⁴ Division of Inorganic Chemistry, Institute of Chemistry, Baghdad-ul-Jadeed Campus, The Islamia University of Bahawalpur, Bahawalpur, 63100, Pakistan.
⁵ Department of Chemistry, University of Agriculture, 38000, Faisalabad, Pakistan.
⁶ Department of Zoology, College of Science, King Saud University, PO Box 2455, Riyadh, 11451, Saudi Arabia.
⁷ Department of Life Sciences, Yeungnam University, Gyeongsan, 38541, Republic of Korea.
⁸ Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, São Paulo, 05508-000, Brazil.

Abstract

The organic compounds are known as an emerging class in the field of nonlinear optical (NLO) materials. In this paper, D-π-A configured oxygen containing organic chromophores (FD2-FD6) were designed by incorporating various donors in the chemical structure of FCO-2FR1. This work is also inspired by the feasibility of FCO-2FR1 as an efficient solar cell. Theoretical approach involving DFT functional i.e., B3LYP/6-311G(d,p) was utilized to achieve useful information regarding their electronic, structural, chemical and photonic properties. The structural modifications revealed significant electronic contribution in designing HOMOs and LUMOs for the derivatives with lowered energy gaps. The lowest HOMO-LUMO band gap obtained was 1.223 eV for FD2 compound in comparison to the reference molecule (FCO-2FR1) i.e., 2.053 eV. Moreover, the DFT findings revealed that the end-capped substituents play a key role in enhancing the NLO response of these push-pull chromophores. The UV-Vis spectra of tailored molecules revealed larger λ _max values than the reference compound. Furthermore, strong intramolecular interactions showed the highest stabilization energy (28.40 kcal mol^-1) for FD2 in the natural bond orbitals (NBOs) transitions, combined with the least binding energy (-0.432 eV). Successfully, the NLO results were favorable for the same chromophore (FD2) which showed the highest value for dipole moment (μ _tot = 20.049 D) and first hyper-polarizability (β _tot = 11.22 × 10^-27 esu). Similarly, the largest value for linear polarizability ⟨α⟩ was obtained as 2.936 × 10^-22 esu for FD3 compound. Overall, the designed compounds were calculated with greater NLO values as compared to FCO-2FR1. The current study may provoke the researchers towards designing of highly efficient NLO materials via using the suitable organic linking species.

Keywords: DFT; Density of states; Hyper-polarizability; Non-fullerene; Second-order NLO response.