Effects of Temperature, Axial Ligand, and Photoexcitation on the Structure and Spin-State of Nickel(II) Complexes with Water-Soluble 5,10,15,20-Tetrakis(1-methylpyridinium-4-yl)porphyrin

Abstract

Water-soluble metalloporphyrins, depending on the metal center, possess special spectral, coordination, and photochemical features. In nickel(II) porphyrins, the Ni(II) center can occur with low-spin or high-spin electronic configuration. In aqueous solution, the cationic nickel(II) complex (Ni(II)TMPyP4+, where H2TMPyP4+ = 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin), exists in both forms in equilibrium. In this study, an equilibrium system involving the low-spin and high-spin forms of Ni(II)TMPyP4+ was investigated via application of irradiation, temperature change, and various potential axial ligands. Soret band excitation of this aqueous system, in the absence of additional axial ligands, resulted in a shift in the equilibrium toward the low-spin species due to the removal of axial solvent ligands. The kinetics and the thermodynamics of the processes were also studied via determination of the rate and equilibrium constants, as well as the ΔS, ΔH, and ΔG values. Temperature increase had a similar effect. The equilibrium of the spin isomers was also shifted by decreasing the solvent polarity (using n-propanol) as well as by the addition of a stronger coordinating axial ligand (such as ammonia). Since triethanolamine is an efficient electron donor in Ni(II)TMPyP4+-based photocatalytic systems, its interaction with this metalloporphyin was also studied. The results promote the development of efficient photocatalytic systems based on this complex.

Keywords

• cationic nickel(II) porphyrin
• square planar
• high spin
• low spin
• spin-state equilibrium
• photoinduced shift