Synthesis, photophysical, structural and electronic properties of novel regioisomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives

Ozser M. E. , Mohiuddin O.

JOURNAL OF MOLECULAR STRUCTURE, vol.1158, pp.145-155, 2018 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 1158
  • Publication Date: 2018
  • Doi Number: 10.1016/j.molstruc.2018.01.023
  • Page Numbers: pp.145-155
  • Keywords: Perylene diimide, Sensitizer, Photophysical properties, Organic photovoltaic, DFT, GAUSSIAN-BASIS SETS, PERYLENE DIIMIDES, ATOMS LI, DENSITY, SUBSTITUENTS, NAPHTHALENE


Three new isomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives namely; N-[2-(diethylamino)ethy1]-1,7-dibromoperylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-1), N-[2-(diethylamino)ethy1]-1,7-di(4-tert-butylphenoxy)perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-2) and N-[2-(diethylamino)ethy1]-1,7-di(pyrrolidinyl) perylene-3,4,9,10-tetracarboxy monoimide dibutylester (PMD-3), have been synthesized and their electronic absorption spectra, and steady-state fluorescence were investigated experimentally as well as by using density functional theory (DFT) calculations. All three compounds show good solubility in toluene and chloroform. Attachment of two tert-butylphenoxy groups at the 1,7-positions in PMD-2 resulted in a red shifted absorption band with an absorption maximum at 518 nm. UV/Vis absorption spectrum of PMD-3 bearing electron donating pyrrolidinyl groups at the 1,7-positions shows a broad absorption band within the visible region, extending to red region. Absorption maximum of lowest energy transition now shifts to 653 nm. In addition to the S-0 -> S-1 absorption bands, bands belonging to S-0 -> S-2 electronic transitions were observed at 378, 386, and 411 nm for PMD-1, PMD-2, and PMD-3 respectively. Compounds PMD-1, PMD-2 and PMD-3 display low fluorescence quantum yields of 0.027, 0.040 and 0.001, respectively in chloroform. DFT calculations revealed that the attachment of electron donating groups at 1,7-positions of perylene core, results in an increase in frontier orbitals energy levels. Observed energy increase in HOMO level is larger in each case, compared to the energy increase in LUMO levels, due to the higher contribution of side groups to HOMO. DFT calculated band gaps for PMD-1, PMD-2 and PMD-3 are 2.68, 2.63 and 2.29 eV respectively. (C) 2018 Elsevier B.V. All rights reserved.