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Isolation and characterization of conformational isomers of N , N ′‐bis(3,5‐dichlorosalicylidene)‐2,2′‐ethylenedianiline: crystal structure, photoluminescence, and density functional theory calculation
Author(s) -
Min Kil Sik,
Kim Yoon Jae,
Ko Hyun Jin,
Kwak Dae Hyun,
Kim Tae Wook,
Shin Jong Won,
Kim Bong Gon
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3379
Subject(s) - chemistry , density functional theory , homo/lumo , crystallography , molecule , crystal structure , crystal (programming language) , fluorescence , photoluminescence , molecular orbital , thermogravimetric analysis , computational chemistry , materials science , optics , organic chemistry , physics , computer science , programming language , optoelectronics
We have isolated two isomeric solids 1 and 2 of N , N ′‐bis(3,5‐dichlorosalicylidene)‐2,2′‐ethylenedianiline and characterized by IR, UV/Vis, X‐ray powder diffraction , thermogravimetric analysis/differential thermal analysis, and X‐ray crystallography. Although the solids are same formulas, each shows different colors and crystal structures. Orange solid ( 1 ) shows endo conformation while yellow solid ( 2 ) exhibits exo form depending on packing modes. UV/Vis spectra of 1 and 2 appear very similar patterns in the solid state; however, the bands of 1 are slightly red‐shifted compared with those of 2 . 1 displays a strong fluorescent emission band at ~582 nm while 2 shows an intense fluorescent signal at ~563 nm. The charge density populations of 1 and 2 have been studied by computational simulations using density functional theory at pbe1pbe/6‐311G** level. The calculated highest occupied molecular orbital and lowest unoccupied molecular orbital energies of 1 and 2 confirm that charge transfer occurs within the organic molecules. The energy difference of HOMO‐LUMO in 1 is smaller slightly than that of 2 about 0.05 eV (~17 nm). Copyright © 2014 John Wiley & Sons, Ltd.