Thermo- and photo-induced electron transfer in a series of [Fe2Co2] capsules

Abstract

Recently, a family of [Fe₂Co₂] molecular capsules that display tunable electron transfer-coupled spin transition (ETCST) behavior were reported via a smart approach through Schiff-base condensation of aldehyde-functionalized 2,2-bipyridines (bpy^CHO) and 1,7-heptanediamine (H₂N(CH₂)₇NH₂). Here, three more capsule complexes {[(Tp^R)Fe(CN)₃]₂[Co(bpy^{CN(CH₂)_nNC}bpy)]₂[ClO₄]₂}·n(solvent) (1, Tp^R = Tp*, n = 5, sol = 8DMF; 2, Tp^R = Tp^Me, n = 9, sol = 5MeCN; and 3, Tp^R = Tp*, n = 11, sol = 5MeCN), where Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate and Tp^Me = hydridotris(3-methylpyrazol-1-yl)borate are reported, demonstrating a successful extension of such an approach with other alkyldiamines of different lengths. Combined X-ray crystallographic, infrared spectroscopic and magnetic studies reveal incomplete electron transfer with either changing temperature or upon light exposure.