Electron Donor and Acceptor Influence on the Nonlinear Optical Response of Diacetylene-Functionalized Organic Materials (DFOMs): Density Functional Theory Calculations

Muhammad Khalid; Riaz Hussain; Ajaz Hussain; Bakhat Ali; Farrukh Jaleel; Muhammad Imran; Mohammad Ali Assiri; Muhammad Usman Khan; Saeed Ahmed; Saba Abid; Sadia Haq; Kaynat Saleem; Shumaila Majeed; Chaudhary Jahrukh Tariq

doi:10.3390/molecules24112096

Electron Donor and Acceptor Influence on the Nonlinear Optical Response of Diacetylene-Functionalized Organic Materials (DFOMs): Density Functional Theory Calculations

Molecules. 2019 Jun 2;24(11):2096. doi: 10.3390/molecules24112096.

Authors

Affiliations

¹ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
² Department of Chemistry, University of Education Lahore, D.G. Khan Campus, Dera Ghazi Khan 32200, Pakistan. [email protected].
³ Institute of Chemical Sciences, Bahauddin Zakariya University, Multan 60800, Pakistan. [email protected].
⁴ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
⁵ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
⁶ Department of Chemistry, Faculty of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia. [email protected].
⁷ Department of Chemistry, Faculty of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia. [email protected].
⁸ Department of Applied Chemistry, Government College University, Faisalabad 38000, Pakistan. [email protected].
⁹ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
¹⁰ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
¹¹ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
¹² Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
¹³ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].
¹⁴ Department of Chemistry, Khwaja Fareed University of Engineering & Information Technology, Rahim Yar Khan 64200, Pakistan. [email protected].

Abstract

Herein, we report the quantum chemical results based on density functional theory for the polarizability (α) and first hyperpolarizability (β) values of diacetylene-functionalized organic molecules (DFOM) containing an electron acceptor (A) unit in the form of nitro group and electron donor (D) unit in the form of amino group. Six DFOM 1-6 have been designed by structural tailoring of the synthesized chromophore 4,4'-(buta-1,3-diyne-1,4-diyl) dianiline (R) and the influence of the D and A moieties on α and β was explored. Ground state geometries, HOMO-LUMO energies, and natural bond orbital (NBO) analysis of all DFOM (R and 1-6) were explored through B3LYP level of DFT and 6-31G(d,p) basis set. The polarizability (α), first hyperpolarizability (β) values were computed using B3LYP (gas phase), CAM-B3LYP (gas phase), CAM-B3LYP (solvent DMSO) methods and 6-31G(d,p) basis set combination. UV-Visible analysis was performed at CAM-B3LYP/6-31G(d,p) level of theory. Results illustrated that much reduced energy gap in the range of 2.212-2.809 eV was observed in designed DFOM 1-6 as compared to parent molecule R (4.405 eV). Designed DFOM (except for 2 and 4) were found red shifted compared to parent molecule R. An absorption at longer wavelength was observed for 6 with 371.46 nm. NBO analysis confirmed the involvement of extended conjugation and as well as charge transfer character towards the promising NLO response and red shift of molecules under study. Overall, compound 6 displayed large α and β_tot, computed to be 333.40 (a.u) (B3LYP gas), 302.38 (a.u.) (CAM-B3LYP gas), 380.46 (a.u.) (CAM-B3LYP solvent) and 24708.79 (a.u), 11841.93 (a.u.), 25053.32 (a.u) measured from B3LYP (gas), CAM-B3LYP (gas) and CAM-B3LYP (DMSO) methods respectively. This investigation provides a theoretical framework for conversion of centrosymmetric molecules into non-centrosymmetric architectures to discover NLO candidates for modern hi-tech applications.

Keywords: NLO properties; density functional theory (DFT); diacetylene-based compounds; quantum chemical study.

MeSH terms

Algorithms
Density Functional Theory*
Electrons*
Models, Molecular
Molecular Conformation
Molecular Structure
Organic Chemicals / chemistry*
Spectrum Analysis
Static Electricity

Substances

Organic Chemicals