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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

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

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Autor(es):
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]
Número total de Autores: 8
Afiliação do(s) autor(es):
[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
Número total de Afiliações: 6
Tipo de documento: Artigo Científico
Fonte: Inorganica Chimica Acta; v. 486, p. 162-171, FEB 24 2019.
Citações Web of Science: 10
Resumo

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)

Processo FAPESP: 15/01491-3 - Estudo teórico das reações de acoplamento-cruzado: catálise homogênea e heterogênea
Beneficiário:Ataualpa Albert Carmo Braga
Linha de fomento: Auxílio à Pesquisa - Regular
Processo FAPESP: 14/25770-6 - Novas fronteiras em reações de acoplamento cruzado mediadas por paládio: associando catálise enantiosseletiva, ativações C-H, novos materiais e reações em fluxo visando alta eficiência e sustentabilidade em processos sintéticos
Beneficiário:Carlos Roque Duarte Correia
Linha de fomento: Auxílio à Pesquisa - Temático