Heterocyclic Donor Moiety Effect on Optical Nonlinearity Behavior of Chrysene-Based Chromophores with Push-Pull Configuration via the Quantum Chemical Approach

Faiz Rasool; Gang Wu; Iqra Shafiq; Shehla Kousar; Saba Abid; Norah Alhokbany; Ke Chen

doi:10.1021/acsomega.3c07596

Heterocyclic Donor Moiety Effect on Optical Nonlinearity Behavior of Chrysene-Based Chromophores with Push-Pull Configuration via the Quantum Chemical Approach

ACS Omega. 2024 Jan 8;9(3):3596-3608. doi: 10.1021/acsomega.3c07596. eCollection 2024 Jan 23.

Authors

Faiz Rasool¹, Gang Wu², Iqra Shafiq^{3

4}, Shehla Kousar^{3

4}, Saba Abid^{3

4}, Norah Alhokbany⁵, Ke Chen²

Affiliations

¹ Institute of Chemical Sciences, Bahauddin Zakariya University, Multan 60800, Pakistan.
² Department of Infectious Diseases, The Affiliated Hospital of Southwest Medical University, Luzhou 646000, China.
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 Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia.

Abstract

Organic-based nonlinear optical (NLO) materials may be used in many optical-electronic systems and other next-generation defense technologies. With the importance of NLO materials, a series of push-pull architecture (D-π-A) derivatives (DTMD2-DTMD6) were devised from DTMR1 through structural alteration of different efficient donor heterocyclic groups. Density functional theory-based computations were executed at the MPW1PW91/6-31G(d,p) level to explore the NLO behavior of the derivatives. To investigate the optoelectronic behavior of the said compounds, various analyses like the frontier molecular orbital (FMO), global reactivity parameters, density of state (DOS), absorption spectra (UV-vis), natural bond orbital, and transition density matrix (TDM) were performed. The derivatives have a smaller band gap (2.156-1.492 eV) and a larger bathochromic shift (λ_max = 692.838-969.605 nm) as compared to the reference chromophore (ΔE = 2.306 eV and λ_max = 677.949 nm). FMO analysis revealed substantial charge conduction out of the donor toward the acceptor via a spacer that was also shown by TDM and DOS analyses. All derivatives showed promising NLO results, with the maximum amplitude of linear polarizability ⟨α⟩ and first (β_total) and second (γ_total) hyperpolarizabilities over their reference chromophore. DTMD2 contained the highest β_total (7.220 × 10^-27 esu) and γ_total (1.720 × 10^-31 esu) values corresponding with the reduced band gap (1.492 eV), representing potential futures for a large NLO amplitude. This structural modification through the use of various donors has played a significant part in achieving promising NLO behavior in the modified compounds.