Inter- and intramolecular interactions of polymers as studied by fluorescence spectroscopy. 9. Synthesis of a polymethacrylate having 2-[(1-pyrenyl)methyl]-2-[4-(dimethylamino)benzyl]ethyl side chains and its exciplex emission behavior

1982 ◽  
Vol 15 (2) ◽  
pp. 396-400 ◽  
Author(s):  
Yoshiaki Iwaya ◽  
Shigeo Tazuke
Keyword(s):  
Fluorescence Spectroscopy ◽  
Intramolecular Interactions ◽  
Side Chains ◽  
Exciplex Emission ◽  
Emission Behavior

scholarly journals Modeling and characterization of exciplexes in photoredox CO2 reduction: Insights from quantum chemistry and fluorescence spectroscopy

2021 ◽  
Author(s):  
Kareesa Kron ◽  
Jonathan Ryan Hunt ◽  
Jahan Dawlaty ◽  
Shaama Mallikarjun Sharada
Keyword(s):  
Excited State ◽  
Fluorescence Spectroscopy ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Co2 Reduction ◽  
Energy Decomposition Analysis ◽  
Emission Frequency ◽  
Exciplex Formation ◽  
Exciplex Emission

Interactions between excited state arenes and amines can lead to the formation of structures with distinct emission behavior. These excited state complexes or exciplexes can reduce the ability of the arene to participate in other reactions, such as CO2 reduction, or increase the likelihood of degradation via Birch reduction. Exciplex geometries are necessary to understand photophysical behavior and probe degradation pathways but are challenging to calculate. We establish a detailed computational protocol for calculation, verification, and characterization of exciplexes. Using fluorescence spectroscopy, we first demonstrate the formation of exciplexes between excited state oligo-(p-phenylene) (OPP), shown to successfully carry out CO2 reduction, and triethylamine (TEA). Time-dependent density functional theory (TDDFT) is employed to optimize the geometries of these exciplexes, which are validated by comparing both emission energies and their solvatochromism with experiment. Excited state energy decomposition analysis confirms the predominant role played by charge transfer interactions in the red-shift of emissions relative to the isolated excited state OPP*. We find that although the exciplex emission frequency depends strongly on solvent dielectric, the extent of charge separation in an exciplex does not. Our results also suggest that the formation of solvent-separated ionic radical states upon complete electron transfer competes with exciplex formation in higher dielectric solvents, thereby leading to reduced exciplex emission intensities in fluorescence experiments.

Sign in / Sign up

Export Citation Format

Share Document