Spectral Signatures of Perylene Diimide Derivatives: Insights From Theory

Abstract

International audiencePerylene diimides and related compounds (naphthalene diimides, anthracene diimides, etc.) are one of the most important classes of organic dyes. Therefore, the prediction and the rationalization of both their transition energies and the particular shape of their absorption and emission spectra is essential to improve their design. Here, we report the simulations of both adiabatic and vibronic signatures of a series of perylene diimide derivatives with a state-of-the-art time-dependent density functional theory (TD-DFT) approach. First, the 0-0 energies have been computed and compared to experimental data. In a second stage, the determination of vibronic shapes has been performed to shed light on the vibrational modes implied in the experimental band topologies. Both anharmonicity and fimctionnal effects are also discussed. It turns out that theory consistently reproduced 0-0 energies but does not always yield band shapes in perfect match with experiment. In a last stage, new structures are designed, and it is shown that a full push effect is more effective than a push-pull strategy for the present class of molecules

Substituent effects on the optical properties of naphthalenediimides: A frontier orbital analysis across the periodic table

“…The computational method used is based on the time‐dependent extension of density functional theory as implemented in the software package ADF . Coupling of the vibrations with the electronic structure were neglected; they have been reported for NDI . The adiabatic local density approximation (ALDA) was used for the xc kernel.…”

“…[44] Coupling of the vibrations with the electronic structure were neglected; they have been reported for NDI. [45] The adiabatic local density approximation (ALDA) was used for the xc kernel. The groundstate KS equations were solved with the recently implemented range-separated hybrid functional CAMY-B3LYP [46,47] with the TZ2P basis set.…”

Physical Vapor Deposited Films of a Perylene Derivative: Supramolecular Arrangement and Thermal Stability

“…14 In Figure 2, the different absorption maxima are assigned to transitions from the ground electronic state (E 0 ) to vibronic progressions of the first electronic excited state (E 1 ). [23][24][25][26] In relation to the UV-Vis absorption spectrum of the PhPTCD solution reported by Constantino et al, 18 the PhPTCD PVD film presents a displacement of the absorption bands for both higher and shorter wavelengths (splitting). This fact can be explained by the model reported by Kasha et al 27,28 The model proposes the splitting of the excited electronic state of a monomer (a molecule) in two other electronic excited states for dimers (two molecules), according to the interaction of the dipole moment of the molecule with the neighboring molecule.…”

Novel nanosized water soluble fluorescent micelles with embedded perylene diimide fluorophores for potential biomedical applications: Cell permeability, localization and cytotoxicity

“…After stirring for 48 h at room temperature, the PVA-b-PAN copolymer was collected, washed with ethyl acetate and dried in vacuo at 50°C. 1 2.4. Synthesis of perylene-3,4,9,10-tetracarboxylic diimides (2)(3)(4) To a suspension of 2.0 g (5 mmol) perylene-3,4,9,10-tetracarboxylic dianhydride 1 into a mixture of 50 mL of water and 50 mL of n-propanol, 20 mmol of the corresponding primary amine (2.1 mL of N,Ndimethylethylenediamine, 2.0 mL of n-butylamine, or 3.5 mL of 2,2,6,6-tetramethylpiperidin-4-ylamine) was added.…”

“…Perylene-3,4,9,10-tetracarboxylic diimides (PDI) have attracted an increasing interest during the past decades, and this can be traced back to their appealing properties, e.g., high electron affinity, large electron mobility, excellent thermal and oxidative stability, high molar absorptivity and quantum yield of fluorescence [1]. They are easy of synthetic modification [2] and widely used n-type materials for organic electronic devices such as solar cells [3][4][5], field-effect transistors [6][7][8], light-emitting diodes [9][10][11].…”