Synthesis, XRD, spectral (IR, UV-Vis, NMR) characterization and quantum chemical exploration of benzoimidazole-based hydrazones: A synergistic experimental-computational analysis

Author(s)

Rafiq, Muhammad ; Khalid, Muhammad ; Tahir, Muhammad Nawaz ; Ahmad, Muhammad Umair ; Khan, Muhammad Usman ; Naseer, Muhammad Moazzam ; Carmo Braga, Ataualpa Albert ; Muhammad, Shabbir ; Shafiq, Zahid

• Document type: Journal article
• Source: APPLIED ORGANOMETALLIC CHEMISTRY; v. 33, n. 11, p. 17-pg., 2019-08-19.

Abstract

Present study advocates the joint experimental and computational studies of two potent benzoimidazole-based hydrazones with chemical formula C23H18F2N4O (5a) and C25H22FN5O3 (5b). Both 5a and 5b were synthesized and resolved into their crystal structures using SC-XRD for the assessment of bond lengths, bond angles, unit cells and space groups. The structures of 5a and 5b were chemically characterized using infrared (FT-IR), UV-Visible, nuclear magnetic resonance (H-1-NMR and C-13-NMR), EIMS and elemental analysis. DFT at M06-2X/6-31G(d,p) level of theory was performed to get optimized structures and countercheck the experimental findings. Overall, DFT findings show excellent concurrence with the experimental data which confirms the purity of both compounds. FMO, NBO analysis, MEP surfaces and nonlinear optical (NLO) properties were explored at same level of theory. UV-Vis analysis at TDDFT/M06-2X/6-31G(d,p) level of theory showed that 5b is red shifted with lambda(max) 331.69 nm as compared to 5a with lambda(max) 240.25 nm. Global reactivity parameters were estimated using energy of FMOs indicated the greater harness value than the softness values of 5a and 5b. NBO analysis confirmed that the presence of non-covalent interactions, hydrogen bonding and hyper conjugative interactions are pivotal cause for the existence of 5a and 5b in the solid-state. NLO results of 5a and 5b were observed better than standard molecule recommended the NLO activity of said molecules for optoelectronic applications. (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
• FAPESP's process: 11/07895-8 - Theoretical study of the Heck-Matsuda reactions
• Grantee: Ataualpa Albert Carmo Braga
• Support Opportunities: Scholarships in Brazil - Post-Doctoral