Synthesis, electrochemistry, protonation and X-ray analysis of meso-aryl substituted open-chain pentapyrroles

Five meso-tetraaryl open-chain pentapyrroles were synthesized and characterized as to their electrochemistry and protonation reactions in nonaqueous media. The investigated compounds are represented as (Ar) 4 PPyH 3 where Ar [Formula: see text],[Formula: see text]-F 2 Ph, [Formula: see text]-BrPh, Ph, [Formula: see text],[Formula: see text],[Formula: see text]-(OMe) 3 Ph or [Formula: see text]-MePh and were characterized by UV-vis and 1 H NMR spectroscopy, mass spectrometry and electrochemistry. Cyclic voltammetry was used to measure redox potentials, while protonation involving the conversion of (Ar) 4 PPyH 3 to [(Ar) 4 PPyH 5 ][Formula: see text] was monitored by UV-vis absorption spectroscopy. Equilibrium constants for proton addition were calculated using the Hill equation. One of the pentapyrroles was also structurally characterized. The electrochemical data, protonation constants and crystal structure were then compared with data for previously examined pentapyrroles and analyzed as a function of the solvent properties and nature of substituents on the meso-phenyl rings of the macrocycle.