Synthesis of New Cobalt(III) Meso-Porphyrin Complex,Photochemical, X-ray Diffraction,and Electrical Properties for Photovoltaic Cells

The present work describes the preparation and characterization of a new cobalt(III) porphyrin coordination compound named (chlorido)(nicotinoylchloride)[meso-tetra(para-chlorophenyl)porphyrinato]cobalt(III) dichloromethane monosolvate with the formula [Co^III(TClPP)Cl(NTC)]·CH₂Cl₂ (4). The single-crystal X-ray molecular structure of 4 shows very important ruffling and waving distortions of the porphyrin macrocycle. The Soret and Q absorption bands of 4 are very red-shifted as a consequence of the very distorted porphyrin core. This coordination compound was also studied by fluorescence and cyclic voltammetry. The efficiency of our four porphyrinic compounds—the H₂TClPP (1) free-base porphyrin, the [Co^II(TClPP)] (2) and [Co^III(TClPP)Cl] (3) starting materials, and the new Co(III) metalloporphyrin [Co^III(TClPP)Cl(NTC)]·CH₂Cl₂ (4)—as catalysts in the photochemical degradation was tested on malachite green (MG) dye. The current voltage of complexes 3 and 4 was also studied. Electrical parameters, including the saturation current density (J_s) and barrier height (ϕ_b), were measured.     

CO2 to CO Electroreduction,Electrocatalytic H2 Evolution,and Catalytic Degradation of Organic Dyes Using a Co(II) meso-Tetraarylporphyrin

The meso-tetrakis(4-(trifluoromethyl)phenyl)porphyrinato cobalt(II) complex [Co(TMFPP)] was synthesised in 93% yield. The compound was studied by ¹H NMR, UV-visible absorption, and photoluminescence spectroscopy. The optical band gap Eg was calculated to 2.15 eV using the Tauc plot method and a semiconducting character is suggested. Cyclic voltammetry showed two fully reversible reduction waves at E_1/2 = −0.91 V and E_1/2 = −2.05 V vs. SCE and reversible oxidations at 0.30 V and 0.98 V representing both metal-centred (Co(0)/Co(I)/Co(II)/Co(III)) and porphyrin-centred (Por²⁻/Por⁻) processes. [Co(TMFPP)] is a very active catalyst for the electrochemical formation of H₂ from DMF/acetic acid, with a Faradaic Efficiency (FE) of 85%, and also catalysed the reduction of CO₂ to CO with a FE of 90%. Moreover, the two triarylmethane dyes crystal violet and malachite green were decomposed using H₂O₂ and [Co(TMFPP)] as catalyst with an efficiency of more than 85% in one batch.