Five Covalent Organic Frameworks (COFs) were synthesized and applied to Dye-Sensitized Solar Cells (DSSCs) as dyes and additives. These porous nanomaterials are based on cheap, abundant commercially available ionic dyes (thionin acetate RIO-43, Bismarck brown Y RIO-55 and pararosaniline hydrochloride RIO-70), and antibiotics (dapsone RIO-60) are used as building blocks. The reticular innovative organic framework RIO-60 is the most promising dye for DSSCs. It possesses a short-circuit current density (J_sc) of 1.00 mA/cm², an open-circuit voltage (V_oc) of 329 mV, a fill factor (FF) of 0.59, and a cell efficiency (η) of 0.19%. These values are higher than those previously reported for COFs in similar devices. This first approach using the RIO family provides a good perspective on its application in DSSCs as a dye or photoanode dye enhancer, helping to increase the cell’s lifespan.

This contribution presents four dye-based CONs derived from the reaction of triformylphloroglucinol with thionin acetate (RIO-43), safranin chloride (RIO-51), phenosafranin (RIO-47), and Bismarck brown Y (RIO-55). These materials, called Covalent Organic Networks (CONs), are insoluble solids formed by organic lamellar stacked structures and present permanent porosity, light absorption across the whole visible spectrum, fluorescence, ion exchange capability, and ion and electron conductivity. Periodic DFT calculations carried out indicated that the bent nature of most of those building blocks affords conductive extended materials containing pores with the shape of three-petal flowers, with the anion positioned at the petals. The turbostratic disorder makes only the center of the flower-shaped pores accessible, decreasing the specific surface areas. The material that has a higher surface area is the one derived from thionin acetate (RIO-43), such as the highest electrical conductivity (1.96 × 10^–5 S cm⁻¹), followed by RIO-47 (1.12 × 10^–7 S cm⁻¹), RIO-55 (1.58 × 10^–7 S cm⁻¹) and RIO-51 (3.26 × 10^–7 S cm⁻¹).

Ferrocene-based porous organic polymers (FPOPs) were prepared from phenol-formaldehyde polymer (Bakelite) and phenol as starting materials; and two possible mechanisms for polymerization were discussed. Solid-state ¹³C CP-MAS NMR, FTIR, powder XRD, elemental analysis and ICP (Fe, Na, B) were performed to characterize the prepared materials. The two synthetic approaches produced polymers with different pore sizes: the FPOP synthesized through Bakelite presented a higher surface area (52 m² g⁻¹) when compared to the one obtained by the bottom-up polymerization from phenol (only 5 m² g⁻¹). Thermogravimetric analysis confirmed the thermal stability of the material, which decomposed at 350 °C. Furthermore, cyclic voltammetry (CV) of the new FPOP on modified electrodes, in ACN and 0.1 M TBAP as an electrolyte, showed fully reversible electron transfer, which is similar to that observed for the ferrocene probe dissolved in the same electrolyte. As a proof-of-concept for an electrochromic device, this novel material was also tested, with a color change detected between yellow/brownish coloration (reduced form) and green/blue coloration (oxidized form). The new hybrid FPOP seems very promising for material science, energy storage and electrochromic applications, as well as for plastic degradation.

Ionic Covalent Organic Frameworks are a special subgroup that has risen as promising materials for innovative applications. In parallel, some of the so-called Reticular Innovative Organic compounds (RIOs), which are ionic and non-ionic porous materials have been used with great versatility, for several purposes. In this work, the ionic dye-based RIO-55 was chosen to capture a series of lanthanides (Eu, Gd, Dy, and Tb) from water, observing their affinity with the lattice and the performance of the adsorbent. Thus, the higher adsorbed amount was referred to as Eu³⁺ (Q_max = 370 mg/g), as well as the best affinity (K_L = 5x10^-3), following the Langmuir model. The impregnated Eu³⁺@RIO-55 was used for chemical sensing, capturing dopant molecules (ephedrine and dopamine) from water, showing great performance, even after some reuse cycles. In addition, some initial fluorescence tests were performed using RIO-55 and Eu³⁺@RIO-55 to observe the spectrum before and after lanthanide impregnation.