Abstract
The paramagnetic trinuclear complex trans-[Pt2Fe(piam)4(NH3)4](ClO4)3·H2O (t-Fe) has a half-filled σ-type orbital over Pt–Fe–Pt, making it an excellent option for magnetic assemblies. It was successfully used in synthesizing [{Rh2(O2CCH3)4Cl2}{Pt2Fe(piam)4(NH3)4}2]n(ClO4)4n (1) from t-Fe and [Rh2(O2CCH3)4Cl2], where each trinuclear complex was bridged by Cl− ions aligned as –Pt–Fe–Pt–Cl–Pt–Fe–Pt– with Fe···Fe distance of 10.1 Å. The zigzag chains were further linked by –Rh–Rh– to form a two-dimensional honeycomb sheet. The X-ray photoelectron spectroscopy, electron paramagnetic resonance, and magnetic susceptibilities measurements revealed that the formal metal oxidation states in 1 were Pt(+2), Fe(+3), and Rh(+2), where five unpaired electrons were located on the Fe(+3) atoms. A significant decrease in χT below 40 K was observed, where the theoretical fitting affords the axial zero-field splitting parameter D = 5.23 cm−1 and zJ = −0.12 cm−1.
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