An in-situ spectroscopy investigation of alkali metal interaction mechanism with the imide functional group

Abstract

Organic anode materials have attracted considerable interest owing to their high tunability by adopting various active functional groups. However, the interaction mechanisms between the alkali metals and the active functional groups in host materials have been rarely studied systematically. Here, a widely used organic semiconductor of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) was selected as a model system to investigate how alkali metals interact with imide functional groups and induce changes in chemical and electronic structures of PTCDI. The interaction at the alkali/PTCDI interface was probed by in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near edge X-ray absorption fine structure (NEXAFS), and corroborated by density functional theory (DFT) calculations. Our results indicate that the alkali metal replaces the hydrogen atoms in the imide group and interact with the imide nitrogen of PTCDI. Electron transfer induced gap states and downward band-bending like effects are identified on the alkali-deposited PTCDI surface. It was found that Na shows a stronger electron transfer effect than Li. Such a model study of alkali insertion/intercalation in PTCDI gives insights for the exploration of the potential host materials for alkali storage applications.

Combined spectroscopic and theoretical analysis of the binding of a water-soluble perylene diimide to DNA/RNA polynucleotides and G-quadruplexes

“…The particle Mesh-Ewald method was used to describe long-range interactions [64]. Preliminary energy minimizations were run for 5000 steps with the steepest descent algorithm, followed by a 500 ps equilibration step, in which solute was harmonically restrained with a force constant of 1000 kJ/mol•nm 2 , gradually relaxed in five consecutive steps of 100 ps each, to 500, 200, 100 and 50 kJ/mol•nm 2 . The final production run of 100 ns (200 ns for binding site II) was performed without restraints.…”

“…Perylene diimides (PDIs) derivatives are aromatic dyes which show intense visible light absorption, excellent photostability and high quantum yields. The low reduction potential of PDIs [1] makes them electron acceptors and semiconductors in photoinduced charge transfer reactions; that's why they are studied for applications in the fields of energy storage and photovoltaics [2], [3], luminescent solar concentrators [4], OLEDs [5], nano-scale electronic components [6] and nanosensors [7]. PDIs undergo auto-aggregation, and the aggregates show interesting new photophysical properties arising from π-π coupling [8], [9], [10].…”

A review on photochemical sensors for lithium ion detection: relationship between the structure and performance

“…Aer adding lithium, Li + replaced the hydrogen atoms in the imide group and interacted with the imide nitrogen of PDI. Unlike PTCDA, Li + showed a weak interaction with oxygen of the carbonyl group [90][91][92] (Fig. 7a).…”

Non-passivating Anion Adsorption Enables Reversible Magnesium Redox in Simple Non-nucleophilic Electrolytes

“…According to Figure b, two N 1s peaks at 400.5 and 398.9 eV emerged for the Mg anode soaked with rPDI. The peak located at 400.5 eV was attributed to the imide group of rPDI adsorbed on the Mg surface. − The peak located at 398.9 eV was attributed to the formation of ionic Mg–N bonds, indicating the strong interaction between Mg and adsorbed rPDI. − …”