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

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

Muhammad Khalid  1 , Riaz Hussain  2 , Ajaz Hussain  3 , Bakhat Ali  4 , Farrukh Jaleel  5 , Muhammad Imran  6 , Mohammad Ali Assiri  7 , Muhammad Usman Khan  8 , Saeed Ahmed  9 , Saba Abid  10 , Sadia Haq  11 , Kaynat Saleem  12 , Shumaila Majeed  13 , Chaudhary Jahrukh Tariq  14
Affiliations

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

Muhammad Khalid et al. Molecules. .

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 βtot, 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.

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Conflict of interest statement

The authors declare that they have no conflicts of interest.

Figures

Figure 1
Figure 1
Representation of parent molecule R and designed compounds 1–6.
Figure 2
Figure 2
HOMOs and LUMOs of the studied compounds (R and 1–6).
Figure 2
Figure 2
HOMOs and LUMOs of the studied compounds (R and 1–6).
Figure 3
Figure 3
UV/Visible spectra of the studied compounds R and 1–6.
Figure 4
Figure 4
Diagrams and color scheme of the studied compounds R and 1–6.
Figure 4
Figure 4
Diagrams and color scheme of the studied compounds R and 1–6.
See this image and copyright information in PMC

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