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

Date

2018-04-15

Author

Ozser, Mustafa E.
Mohiuddin, Obaidullah

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

146
views

0
downloads

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.

Subject Keywords

Perylene diimide, Sensitizer, Photophysical properties, Organic photovoltaic

URI

https://hdl.handle.net/11511/64582

Journal

JOURNAL OF MOLECULAR STRUCTURE

DOI

https://doi.org/10.1016/j.molstruc.2018.01.023

Collections

Engineering, Article

Suggestions

OpenMETU
Core

Novel derivatives of regioisomerically pure 1,7-disubstituted perylene diimide dyes bearing phenoxy and pyrrolidinyl substituents: Synthesis, photophysical, thermal, and structural properties Ozser, Mustafa E.; Sarkodie, Samuel A.; Mohiuddin, Obaidullah; Ozesme, Gozde (2017-12-01) Two new isomerically pure 1,7-substituted perylene-bisimide derivatives namely; 1,7-Di(4-tert-butylphenoxy)N,N'-bis[2-(diethylamino)ethyl]-3,4,9,10-perylene-tetracarboxylic diimide (6) and 1,7-Di(pyrrolidinyl)-N,N'-bis [2-(diethylamino)ethyl]-3,4,9,10-perylene- tetracarboxylic diimide (7), have been synthesized and their electronic absorption, steady-state fluorescence, and thermal properties were studied. Both compounds show good solubility in a range of organic solvents. Attachment of two electron donatin...
Synthesis and electropolymerization of an ion sensing and fluorescent fluorene derivative bearing a quinoxaline moiety and its analogues with different donor units KIVRAK, Arif; Carbas, Buket Bezgin; Zora, Metin; Önal, Ahmet Muhtar (Elsevier BV, 2012-09-01) A series of new fluorene derivatives bearing pendant quinoxaline moieties with different donor groups, namely 5'H-spiro[fluorene-9,4'-pyrrolo[1,2-alquinoxaline] (FQ), 2,7-di(thiophen-2-yl)-5'H-spiro[fluorene-9,4'-pyrrolo[1,2-a]quinoxaline] (TQT), 2,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-5'H-spiro[fluorene-9,4'-pyrrolo[1,2-a]quinoxaline] (EQE) and 2,7-bis(3,3-dihexyl-3,4-dihydro-2H-thieno[3,4-b][1,4)dioxepin-6-yl)-5'H-spiro[fluorene-9,4'-pyrrolo[1,2-a]quinoxaline] (PQP) were synthesized. The monomer...
Synthesis of Indolizines by Dimerization of N-Propargylated Pyrroles via Allene Intermediates Kuzu, Burak; Gul, Sergen; Tan Uygun, Meltem; Mengeş, Nurettin; Balcı, Metin (2021-03-01) Ten different N-propargyl pyrrole derivatives having various substituents at the C-2 position were synthesized. These derivatives were converted into indolizine derivatives by the [2+2] cycloaddition reaction of pyrrole N-allene, forming in situ, by heating in PrOH in basic medium. The structures were characterized by NMR and X-ray crystallography. The N-propargylated derivatives smoothly underwent intermolecular cyclizations to produce indolizine derivatives in good yields. We proposed a radical mechanism ...
Synthesis of new 4-aza-indoles via acyl azides Dogan, Sengul Dilem; DEMİRPOLAT, Eren; Aycan, Mukerrem Betul Yerer; Balcı, Metin (Elsevier BV, 2015-01-14) We hereby report the preparation of new azaindole derivatives starting from 2-(2-ethoxy-2-oxoethyl) nicotinic acid. Conversion of a half ester into acyl azide followed by Curtius rearrangement gave the corresponding isocyanate. Trapping of the isocyanate with different nucleophiles produced urea and urethane derivatives. Intramolecular cyclization reactions gave the target compounds.
Synthesis of 1,4-Thiazepines Kelgokmen, Yılmaz; Zora, Metin (American Chemical Society (ACS), 2018-08-03) An efficient, general, and unprecedented methodology for the synthesis of 2-methylene-2,3-dihydro-1,4-thiazepines from N-propargylic beta-enaminones is described. Initially, N-propargylic beta-enaminones were thionated with Lawesson's reagent in good to high yields, and then the resulting N-propargylic beta-enaminothiones were subjected to electrophilic cyclization. When treated with zinc chloride in refluxing chloroform, Npropargylic beta-enaminothiones underwent electrophilic cyclization to yield 2-methyl...

Citation Formats

M. E. Ozser and O. Mohiuddin, “Synthesis, photophysical, structural and electronic properties of novel regioisomerically pure 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic monoimide dibutylester derivatives,” JOURNAL OF MOLECULAR STRUCTURE, pp. 145–155, 2018, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/64582.