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 thePTC-TMCPs, 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 ofPTC-Znwere
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 onPTC-TMsshowed 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.