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Issue 39, 2011
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Photophysical and quantum chemical study on a J-aggregate forming perylene bisimide monomer

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Abstract

Perylene bisimides (PBIs) are excellent dyes and versatile building blocks for supramolecular structures. Only recently have PBIs been shown to depict absorption characteristics of J-aggregates. We apply electronic structure calculations and femtosecond pump–probe spectroscopy to the monomeric, bay-substituted building-block of a PBI aggregate in dichloromethane to investigate its electronically excited states in order to provide the ingredients for the description of excitons in the aggregates and their annihilation processes. The PBI S1 ← S0absorption spectrum and the S1 → S0emission spectrum have been assigned based on time-dependent Density Functional Theory calculations for the geometry-optimized electronic ground state and excited state structures in the gas phase. The monomeric absorption spectrum contains a strong transition at 580 nm and a broad shoulder between 575–500 nm, both features are attributed to a vibrational progression with an effective vibrational mode of 1415 cm−1 whose major contributing vibrational normal modes are breathing modes of the perylene body. The effective vibrational mode of the emission spectrum is characterized by a frequency of 1369 cm−1, whose major contributing vibrational normal modes are characterized by perylene and phenol (bay-substituent) CH bendings. The Sn ← S1 excited state absorption spectrum is assigned based on Multi-Reference Configuration Interaction methodology. Here, we identify three transitions which give rise to two broad experimental features, one being located between 500 and 600 nm and the other one ranging from 650 to 750 nm.

Graphical abstract: Photophysical and quantum chemical study on a J-aggregate forming perylene bisimide monomer

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Supplementary files

Article information


Submitted
20 May 2011
Accepted
12 Aug 2011
First published
07 Sep 2011

Phys. Chem. Chem. Phys., 2011,13, 17649-17657
Article type
Paper

Photophysical and quantum chemical study on a J-aggregate forming perylene bisimide monomer

D. Ambrosek, H. Marciniak, S. Lochbrunner, J. Tatchen, X. Li, F. Würthner and O. Kühn, Phys. Chem. Chem. Phys., 2011, 13, 17649
DOI: 10.1039/C1CP21624D

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