A facile synthesis and structural elucidation for furfural based chromophores: Prediction of linear and nonlinear optical properties

Author(s)

Jawaria, Rifat ^[1] ; Khalid, Muhammad ^[1] ; Khan, Jallat ^[1] ; Khan, Muhammad Usman ^[2] ; Carmo Braga, Ataualpa Albert ^[3] ; Zahoor, Sidra ^[1] ; Alam, Mohammed Mujahid ^[4] ; Imran, Muhammad ^[4]

Affiliation

^[1] Khwaja Fareed Univ Engn & Informat Technol, Dept Chem, Rahim Yar Khan 64200 - Pakistan

^[2] Univ Okara, Dept Chem, Okara 56300 - Pakistan

^[3] Univ Sao Paulo, Dept Quim Fundamental, Inst Quim, Ave Prof LineuPrestes 748, BR-05508000 Sao Paulo - Brazil

^[4] King Khalid Univ, Fac Sci, Dept Chem, POB 9004, Abha 61413 - Saudi Arabia

• Document type: Journal article
• Source: Journal of Molecular Structure; v. 1249, FEB 5 2022.
• Web of Science Citations: 0

Abstract

A facile condensation reaction between thiosemicarbazide and furfural was accomplished to synthe-size thiosemicarbazone derivatives: TMOH, FMOH, TMEH, FMEH, DCFH and DCMH with good yields as 73%, 70%, 72%,71%, 74% and 74%, respectively. They were characterized by spectroscopic techniques as UV-Vis, FT-IR, 1 H and 13CNMR. Furthermore, density functional theory (DFT) analysis was per-formed by applying M06 level with 6-311G(d,p) basis set for geometry optimization, natural bond or-bitals (NBOs), linear and nonlinear optical (NLO) and vibrational analyses. Time-dependent DFT ap-plying M06/6-311G(d,p) level of theory was used for computing frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP) and UV-Vis analyses. Experimental values of vibrational wave number and Amax values were seen in good correspondence with the DFT-based results. NBO in-vestigation revealed that title compounds were found with prominent hyper-conjugative interac-tions having stabilization energies as 57.72, 62.66, 59.95, 58.54, 63.59 and 45.6 kcal/mol, respectively, which are probably the main reasons for their stability. The descending order of Egap was found as DCMH >DCFH >TMOH >TMEH >FMEH >FMOH. Therefore, FMOH, exhibiting the smallest energy gap of 4.416 eV , can be regarded as an efficiently polarized structure, possessing a high capacity for electron transfer. MEP analysis describes the involvement of various reaction sites in chemical reactivity, at differ-ent portions of spread electronic cloud over the molecule. The decrease in values of (alpha) for title com-pounds are found as DCFH >DCMH >FMOH >TMOH >FMEH >TMEH. Moreover, beta tot values are found with this order DCFH >DCMH >TMOH >TMEH >FMEH >FMOH. It can be seen that DCMH exhibits a larger NLO response with (alpha) and beta tot figured as 300.51 and 2614.07 a.u., respectively. (c) 2021 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 15/01491-3 - Theoretical study of cross-coupling reactions: homogeneous and heterogeneous catalysis
• Grantee: Ataualpa Albert Carmo Braga
• Support Opportunities: Regular Research Grants
• FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
• Grantee: Carlos Roque Duarte Correia
• Support Opportunities: Research Projects - Thematic Grants