Synthesis, crystal structure analysis, spectral characterization and nonlinear optical exploration of potent thiosemicarbazones based compounds: A DFT refine experimental study

Author(s)

Jawaria, Rifat ^[1] ; Hussain, Mazhar ^[2] ; Khalid, Muhammad ^[1] ; Khan, Muhammad Usman ^[3] ; Tahir, Muhammad Nawaz ^[4] ; Naseer, Muhammad Moazzam ^[5] ; Carmo Braga, Ataualpa Albert ^[6] ; Shafiq, Zahid ^[2]

Affiliation

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

^[2] Bahauddin Zakariya Univ, Inst Chem Sci, Multan 60800 - Pakistan

^[3] Govt Coll Univ, Dept Appl Chem, Faisalabad 38000 - Pakistan

^[4] Univ Sargodha, Dept Phys, Sargodha 40100 - Pakistan

^[5] Quaid I Assam Univ, Dept Chem, Islamabad 45320 - Pakistan

^[6] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, Ave Prof Lineu Prestes 748, BR-05508000 Sao Paulo - Brazil

• Document type: Journal article
• Source: Inorganica Chimica Acta; v. 486, p. 162-171, FEB 24 2019.
• Web of Science Citations: 22

Abstract

The thiosemicarbazones have exciting biological and nonlinear optical (NLO) applications. The present study reports detail experimental and computational studies of three novel ferrocene-substituted thiosemicarbazones: (E/Z)-4-benzyl-1-(1-ferrocenylethyl)thiosemicarbazones (1), (E/Z)-4-(4-chlorobenzyl)-1-(1-ferrocenyl-ethyl) thiosemicarbazone (2) and (E/Z)-4-(2-bromo benzyl)-1-(1-ferrocenylethyl)thiosemicarbazone (3). These compounds were synthesized and resolved into their single crystal structures for the estimation of unit cells, space groups, bond angles and bond lengths. Chemical structures of 1-3 were further characterized spectroscopically employing nuclear magnetic resonance technique (1H NMR), infrared (FT-IR), mass and UV-Visible studies. Computational studies of 1-3 were performed using density functional theory (DFT) tools at M06 level of theory and 6-31 + G(d,p) basis set combination to gain the optimized geometry. A good correlation was found between experimental SC-XRD structures and DFT optimized geometries. Electronic properties including natural bond orbital (NBO) analysis, frontier molecular orbitals (FMOs) analysis, spectroscopic FT-IR data and NLO properties were calculated using same M06/6-31 + G(d,p) level of theory. NBO analysis confirmed the formation of charge separation state due to successful migration of electrons from donor to acceptor unit through pi-bridge. Global reactivity parameters were estimated using energies of FMOs which described that 1-3 are chemically hard and stable molecules. Vertical electronic transition states were calculated using time-dependent DFT (TDDFT) at same level of theory. NLO properties of 1-3 were computed 5.77, 3.48 and 8.93 times greater than the standard urea molecule respectively. Two-state model confirmed the potential of synthesized molecules as NLO candidates. (AU)

• 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
• 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