Design and Synthesis of Efficient Electrogenerated Chemiluminescent Emitters Derived from Pyrene

Abstract

The design and synthesis of novel dendrimeric structures derived from a pyrene core with substituted triphenylamine and carbazole periphery demonstrated how molecular engineering allowed the fine tuning of the electrogenerated chemiluminiscence (ECL) properties. These two compound (Py-CBZ and Py-TPA) in comparison with the parent structures (Py and Py-Core) showed better chemical stability and anti-aggregation capability. At the same time, the photophysical ( Abs λ max , E 00 , FL λ max , FL ), photochemical (oxygen quenching), electrochemical (redox potentials) and optoelectronic (HOMO-LUMO gap and their energy position) properties were modulated, resulting in obtaining two highly ECL emitting molecular structures (Py-CBZ and Py-TPA). This study showed that functionalization of organic dyes with redox moieties (with the proper linker and position) improved the radical stability and also, modulated the optoelectronic properties with the concomitant enhancement of the ECL performance and their potential use in applications such as organic light-emitting devices.

Modular Synthesis and Structure–Property Correlation of Pyrene – Rylene Dyes for Cellular Imaging

“…Tetrabutyl 1‐bromoperylene‐3,4,9,10‐tetracarboxylate (PTE‐Br), tetrabutyl perylene‐3,4,9,10‐tetracarboxylate (PTE), 6‐bromo‐2‐dodecyl‐1 H ‐benzo[ de ]isoquinoline‐1,3(2 H )‐dione (NMI‐Br), 1,6‐diethynylpyrene and 1,3,6,8‐tetraethynylpyrene were synthesized according to the cited literature. The synthesis of target compounds are as follows:…”

3D Flower-Like MoS2 Nanomaterial as Signal-Promoter of PTC-PEI/S2O8 2− System for Fabricating a Sensitive Electrochemiluminescence Methotrexate Sensor

“…[1][2][3][4] As a classic ECL luminophores, Perylene derivatives exihibit excellent chemical stability, high luminescent efficiency and admirable membrane-forming properties. [5][6][7][8] However, the ECL emitting of perylene derivatives with S 2 O 8 2− as coreactant is not strong enough to realize trace determination, thus greatly limiting the application of perylene derivatives in ECL biosensor field. 8 Admittedly, improving the concentration of S 2 O 8 2− is a viable strategy to promote the ECL efficiency of perylene derivatives/S 2 O 8 2− system, nevertheless, enhancing the ECL signal of perylene derivatives via increasing the concentration of S 2 O 8 2− is confined by the limited solubility of S 2 O 8 2− and non-linear generation of sulfate radical anion (SO 4 .…”

Monomer and Excimer Emission in Electrogenerated Chemiluminescence of Pyrene and 2,7-Di-tert-butylpyrene Associated with Electron Transfer Distance

“…The narrower HOMO–LUMO energy gap for the oligomers should be energetically favorable to form the excited states of the oligomers through ion annihilation, as demonstrated in Figure . Thus, the lack of the Py monomer component in ECL reported so far − is likely attributable to the generation of Py oligomers, and the broad components likely mainly originate from the oligomer ECL.…”

“…It is well-known that pyrene (Py) dissolved in organic solvents shows both monomer and excimer photoluminescence (PL), whose emission intensity of the monomer and excimer depends on the concentration . On the ECL spectrum of Py, usually, a broad component, which is considered to be the excimer emission, has only been seen, and the monomer emission has not been observed clearly. − This experimental observation implies that the excimer states are produced directly via ion annihilation by a contact ion pair. However, little attention has been paid to the mechanism of excimer emission in ECL, especially which related to the electron transfer distance ( d et ).…”

“…Because of the presence of tert -butyl groups, the electrochemical and photophysical properties, and thus the ECL properties, are expected to be different from those of Py somewhat. There are several systematic research on the ECL properties of Py derivatives by introducing bulky substituents, where the electronic structure of the Py skeleton was largely changed by the extension of π conjugate caused by the substituents. ,,− Hence, the ECL property including the excimer emission of the derivatives was also significantly changed by the steric hindrance and the π conjugate. Compared to the substituents, tert -butyl groups change the electronic structure of Py moiety less.…”