Linear Photophysics, Stimulated Emission, And Ultrafast Spectroscopy Of New Two-Photon Absorbing Diketopyrrolopyrrole Derivatives

Abstract

The synthesis and comprehensive linear photophysical and nonlinear optical characterization of new diketopyrrolopyrrole derivatives, 2-(2-ethylhexyl)-3,6-di(pyridin-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (1) and 2-(10-azidodecyl)-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (2), are reported. The nature of the main linear absorption bands of 1 and 2 was ascertained based on experimental excitation anisotropy spectra and quantum chemical calculations. Three-dimensional fluorescence maps, emission lifetimes, and photochemical decomposition quantum yields of the new derivatives were obtained in a number of organic solvents at room temperature. Two-photon absorption (2PA) spectra of 1 and 2 were measured over a broad spectral range using an open aperture Z-scan technique, revealing a maximum 2PA cross section of ∼100 GM. Transient absorption and stimulated emission pump-probe measurements with femtosecond time resolution revealed two different types of fast relaxations in the excited states of 1 and 2, and one-photon stimulated emission depletion (STED) spectra were determined. Efficient superfluorescence emission of 1 was observed under femtosecond transverse pumping conditions. A quantum-mechanical investigation of the electronic structure of the new compounds was performed using TD-DFT methodology. Simulated linear absorption spectra, including Franck-Condon band structure of the first excited states, were found in good agreement with experimental data, while 2PA cross sections obtained without vibronic contributions were considerably underestimated.

Publication Date

4-23-2015

Publication Title

Journal of Physical Chemistry C

Volume

119

Issue

16

Number of Pages

8864-8875

Document Type

Article

Personal Identifier

scopus

DOI Link

https://doi.org/10.1021/acs.jpcc.5b00940

Socpus ID

84928485581 (Scopus)

Source API URL

https://api.elsevier.com/content/abstract/scopus_id/84928485581

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