Effect of different end-capped donor moieties on non-fullerenes based non-covalently fused-ring derivatives for achieving high-performance NLO properties

Muhammad Khalid; Iqra Shafiq; Umm-E-Hani; Khalid Mahmood; Riaz Hussain; Muhammad Fayyaz Ur Rehman; Mohammed A Assiri; Muhammad Imran; Muhammad Safwan Akram

doi:10.1038/s41598-023-28118-w

Effect of different end-capped donor moieties on non-fullerenes based non-covalently fused-ring derivatives for achieving high-performance NLO properties

Sci Rep. 2023 Jan 25;13(1):1395. doi: 10.1038/s41598-023-28118-w.

Authors

Muhammad Khalid^{1

2}, Iqra Shafiq^{3

4}, Umm-E-Hani^{3

4}, Khalid Mahmood⁵, Riaz Hussain⁶, Muhammad Fayyaz Ur Rehman⁷, Mohammed A Assiri^{8

9}, Muhammad Imran^{8

9}, Muhammad Safwan Akram^{10

11}

Affiliations

¹ Institute of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan. muhammad.khalid@kfueit.edu.pk.
² Centre for Theoretical and Computational Research, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan. muhammad.khalid@kfueit.edu.pk.
³ Institute of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan.
⁴ Centre for Theoretical and Computational Research, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan, 64200, Pakistan.
⁵ Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, 60800, Pakistan.
⁶ Division of Science and Technology, Department of Chemistry, University of Education, Lahore, Pakistan.
⁷ Institute of Chemistry, University of Sargodha, Sargodha, Pakistan.
⁸ Department of Chemistry, Faculty of Science, King Khalid University, P.O. Box 9004, Abha, 61413, Saudi Arabia.
⁹ Research Center for Advanced Materials Science (RCAMS), King Khalid University, P. O. Box 9004, Abha, 61514, Saudi Arabia.
¹⁰ National Horizons Centre, Teesside University, Darlington, DL11HG, UK. safwan.akram@tees.ac.uk.
¹¹ School of Health and Life Sciences, Teesside University, Middlesbrough, TS1 3BX, UK. safwan.akram@tees.ac.uk.

Abstract

A series of derivatives (DOCD2-DOCD6) with D-π-A configuration was designed by substituting various efficient donor moieties via the structural tailoring of o-DOC6-2F. Quantum-chemical approaches were used to analyze the optoelectronic properties of the designed chromophores. Particularly, M06/6-311G(d,p) functional was employed to investigate the non-linear optical (NLO) response (linear polarizability ⟨α⟩, first (β_tot) and second ([Formula: see text]_tot) order hyperpolarizabilities) of the designed derivatives. A variety of analyses such as frontier molecular orbital (FMO), absorption spectra, transition density matrix (TDMs), density of states (DOS), natural bond orbital (NBO) and global reactivity parameters (GRPs) were employed to explore the optoelectronic response of aforementioned chromophores. FMO investigation revealed that DOCD2 showed the least energy gap (1.657 eV) among all the compounds with an excellent transference of charge towards the acceptor from the donor. Further, DOS pictographs and TDMs heat maps also supported FMO results, corroborating the presence of charge separation states along with efficient charge transitions. NBO analysis showed that π-linker and donors possessed positive charges while acceptors retained negative charges confirming the D-π-A architecture of the studied compounds. The λ_max values of designed chromophores (659.070-717.875 nm) were found to have broader spectra. The GRPs were also examined utilizing energy band gaps of E_HOMO and E_LUMO for the entitled compounds. Among all the derivatives, DOCD2 showed the highest values of β_tot (7.184 × 10^-27 esu) and [Formula: see text]_tot (1.676 × 10^-31 esu), in coherence with the reduced band gap (1.657 eV), indicating future potentiality for NLO materials.