Evidence of protonation induced intra-molecular metal-to-metal charge transfer in a highly symmetric cyanido bridged {Fe2Ni2} molecular square

Abstract

The possibility to induce intra-molecular metal-to-metal charge transfer in a cyanido bridged tetranuclear square shaped {Fe₂Ni₂} complex by employing protonation as an external stimulant is explored. Two cyanido bridged square shaped tetranuclear complexes, [{Ni(TPA)(μ₂-NC)₂Ni(CN)₂}₂]·4H₂O (2) and [{Ni(TPA)(μ₂-NC)₂Fe(bbp)(CN)}₂]·10H₂O (3) [TPA = tris(3,5-dimethylpyrazol-1-ylmethyl)amine and H₂bbp = bis(2-benzimidazolyl)pyridine], are synthesized and characterized. Low temperature magnetic measurements reveal that complex 3 has dominant ferromagnetic interactions between low-spin Fe^III (S = 1/2) and high-spin Ni^II (S = 1) ions. UV-visible spectrophotometric measurements and electrochemical studies establish that reversible intra-molecular metal-to-metal electron transfer can be triggered in 3 upon the addition of either an acid or a base.