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Construction of New Azo‐group Containing Polycyclic Imidazole Derivatives: Computational Mechanistic, Structural, and Fluorescence Studies
Author(s) -
Abdullayev Yusif,
Mammadov Ayaz,
Karimova Nazani,
Talybov Avtandil,
Yolchuyeva Ulviyya,
Autschbach Jochen
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202000949
Subject(s) - imidazole , catalysis , chemistry , ionic liquid , homo/lumo , fluorescence , medicinal chemistry , ring (chemistry) , stereochemistry , molecule , organic chemistry , quantum mechanics , physics
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 ([Me 2 pi][HSO 4 ] 2 ) ionic liquid (IL) catalyst (3 mol%). Mechanistic studies are performed with DFT M06 L functional. The utilized IL catalyst holds two moles of HSO 4 − 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.