Construction of New Azo‐group Containing Polycyclic Imidazole Derivatives: Computational Mechanistic, Structural, and Fluorescence Studies. Issue 20 (28th May 2020)

• Record Type: Journal Article
• Authors: Abdullayev, Yusif; Mammadov, Ayaz; Karimova, Nazani; Talybov, Avtandil; Yolchuyeva, Ulviyya; Autschbach, Jochen
• Is Part Of: ChemistrySelect. Volume 5:Issue 20(2020)
• Page Start: 6224
• Page End: 6229
• Publication Date: 2020-05-28
• Subjects: ionic liquid -- polycyclic imidazole -- DFT -- energy barrier -- transition state -- quantum yield -- energy gap -- fluorophore -- etc.; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202000949
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Three polycyclic aromatic imidazole derivatives 2‐phenyl‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9, 10‐d]imidazole (PRO ), 2‐(4‐methoxyphenyl)‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9, 10‐d]imidazole (PRO1 ), 2‐(2, 4‐dichlorophenyl)‐1‐(4‐(phenyldiazenyl)phenyl)‐1H‐phenanthro[9, 10‐d]imidazole (PRO2 ) are synthesized with one‐pot four component fusion reaction using 1, 4‐dimethylpyperazinium dihydrosulfate ([Me2 pi][HSO4 ]2 ) ionic liquid (IL) catalyst (3 mol%). Mechanistic studies are performed with DFT M06 L functional. The utilized IL catalyst holds two moles of HSO4 − per one mole of 1, 4‐dimethylpyperazinium (cation part), which increases its catalytic performance in a trans form (Figure 1). The IL catalytic effects are determined and described in the optimized transition state structures (Figure 2). Important transition states for the rate‐limiting step (▵G ≠ =26.56 kcal/mol), the five‐membered imidazole ring formation (▵G ≠ =6.9 kcal/mol), and the C(sp 3 )‐H (▵G ≠ =2.06 kcal/mol) activation are optimized. The PRO fluorescence properties are studied computationally (HOMO and LUMO energy gap=2.41 eV) and experimentally. Abstract : A four‐component polycyclic imidazole formation reaction is studied experimentally and computationally in the presence of 1, 4‐dimethylpyperazinium dihydrosulfate ([Me2 pi][HSO4 ]2 ) ionic liquid catalyst (3 mol%). The product fluorescent properties are studied with UV‐vis. and TD‐DFT. The HOMO‐LUMO energy gap studies show that the compound can be utilized as a potential material in optoelectronic devices.