Noncovalent Dualism in Perylene-Diimide-Based Keggin Anion Complexes: Theoretical and Experimental studies

Abstract

We report the synthesis and comprehensive characterization of organic−inorganic hybrid salts formed by bis-cationic N,N′-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD 2+ ) and Keggin-type 3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π−π interactions, contrasting with the previously reported cation−anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π−π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and Xray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic−inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

Fluorescent Nanocomposite Prepared through Supramolecular Self-Assembly of a Tetraphenylethene Derivative and Polyoxometalate for Light-Emitting Diodes

“…Compared with traditional light sources, WLEDs have the advantages of low energy consumption, long life, light weight, and fast response; they are known as the “fourth generation of light sources” and have great application prospects in the field of lighting and display . At present, most of the methods for preparing WLEDs use many types of phosphors and complex steps, and many methods use substances containing sulfur and other elements, which are not friendly to the environment. , In the realm of optoelectronic devices, TPE-1 and EuW 10 have already demonstrated their utility. − As an illustrative example, Feng et al designed and synthesized a series of mixed-additive POMs utilizing pH-neutral counterions, such as NH 4+ , K + , and Na + , as hole transport layer (HTL) materials . Yang et al proposed Dawson-type polyoxometalates (POMs) as innovative anode interlayer materials for organic optoelectronic devices, exhibiting remarkable hole injection/collection capabilities and significantly improving device efficiency …”