Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2010-05-06

Theoretical investigation on the effect of protonation on the absorption and emission spectra of two amine-group-bearing, red "push-pull" emitters, 4-dimethylamino-4'-nitrostilbene and 4-(dicyanomethylene)-2-methyl-6-p-(dimethylamino) styryl-4H-pyran, by DFT and TDDFT calculations.

I D Petsalakis, D G Georgiadou, M Vasilopoulou, G Pistolis, D Dimotikali, P Argitis, G Theodorakopoulos

Index: J. Phys. Chem. A 114 , 5580-5587, (2010)

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Abstract

A theoretical investigation on the electronic structure of 4-dimethylamino-4'-nitrostilbene (DANS), 4-(dicyanomethylene)-2-methyl-6-p-(dimethylamino) styryl-4H-pyran (DCM), and their protonated forms is presented in an effort to rationalize recent experimental results on the tuning of the emitted color of organic light-emitting diodes through photochemically induced protonation. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been carried out on the neutral and protonated forms of DANS and DCM, employing both the B3LYP and the CAM-B3LYP functionals. It was found that the CAM-B3LYP functional leads to better agreement than the B3LYP of the calculated with the experimental absorption lambda(max) for DANS, whereas B3LYP is more appropriate than CAM-B3LYP for DCM. The results of the calculations aid in a rationalization of the observed differences of the spectra of DANS and DCM upon protonation, and in particular those differences that make DANS a more attractive system for absorbance and emission tuning.