Electrically conductive Metal-Organic Frameworks (MOFs) have emerged in the past few years as promising materials towards applications in (opto)electronics, electrocatalysis and energy storage, among others. One of the most common...

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal−organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of great interest due to its potential to introduce both luminescence and redox properties. Herein, we present an innovative synthesis method for producing a family of highly crystalline and stable coordination polymers based on perylene-3,4,9,10-tetracarboxylate (PTC) and various transition metals (TMs = Co, Ni, and Zn) with an isostructural framework. The crystal structure of the PTC-TM CPs, obtained through powder X-ray diffraction and Rietveld refinement, provides valuable insights into the composition and organization of the building blocks within the CP. The perylene moieties are arranged in a herringbone pattern, with short distances between adjacent ligands, which contributes to the dense and highly organized framework of the material. The photophysical properties of PTC-Zn were thoroughly studied, revealing the presence of J-aggregation-based and monomer-like emission bands. These bands were experimentally identified, and their behavior was further understood through the use of quantum-chemical calculations. Solid-state cyclic voltammetry experiments on PTC-TMs showed that the perylene redox properties are maintained within the CP framework. This study presents a simple and effective approach for synthesizing highly stable and crystalline perylene-based CPs with tunable optical and electrochemical properties in the solid state.

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Tetrathiafulvalene is among the best known building blocks in molecular electronics due to its outstanding electron-donating and redox properties. Among its derivatives, dithiophene-tetrathiafulvalene (DT-TTF) has attracted considerable interest in organic electronics, owing to its high field-effect mobility. Herein, we report the direct CÀ H arylation of DT-TTF to synthesise mono-and tetraarylated derivatives functionalised with electron-withdrawing and electron-donating groups in order to evaluate their influence on the electronic properties by cyclic voltammetry, UV-vis spectroscopy and theoretical calculations. Self-assembly of the DT-TTF-tetrabenzoic acid derivative was studied by using scanning tunnelling microscopy (STM) which revealed the formation of ordered, densely packed 2D hydrogen-bonded networks at the graphite/liquid interface. The tetrabenzoic acid derivative can attain a planar geometry on the graphite surface due to van der Waals interactions with the surface and H-bonding with neighbouring molecules. This study demonstrates a simple method for the synthesis of arylated DT-TTF derivatives towards the design and construction of novel π-extended electroactive frameworks.

Synthesis of a new family of arylated dithiophene‐tetrathiafulvalene (DT‐TTF) derivatives. The influence of electron‐donating and electron‐withdrawing substituents on DT‐TTF's electronic properties has been evaluated. Two‐dimensional, hydrogen‐bonded, self‐assembled networks of tetrabenzoic acid derivative at the graphite/liquid interface were visualized by scanning tunneling microscopy. More information can be found in the Research Article by M. Souto and co‐workers (DOI: 10.1002/chem.202300572).