Synthesis and Structures of Fe III Complexes Bridged by Cyanorhenium Clusters

The reaction of FeCl(L1) and FeCl(L2) [L1 = bis(3‐salicylideneaminopropyl)amine, L2 = bis(3‐salicylideneaminopropyl)methylamine] with the Re 6 clusters [Re 6 Q 8 (CN) 6 ] 4− (Q = Se, Te) led to the formation of the nanomolecular (≈2.5 nm) compounds [(CN) 2 Re 6 Se 8 {(CN)Fe(L1)} 4 ]·7H 2 O ( 1 ) and [(CN) 2 Re 6 Te 8 {(CN)Fe(L2)} 4 ]·4CH 3 CN·4H 2 O ( 2 ). Both compounds were characterized by single‐crystal X‐ray diffraction analysis. Compound 1 crystallizes in the triclinic space group P $\bar 1$ with a = 12.2822(10), b = 14.2524(10), c = 15.8474(10) Å, α = 106.093(10)°, β = 101.992(10)°, γ = 92.438(10)°, and Z = 1. Compound 2 crystallizes in the orthorhombic space group Pbca with a = 19.3024(2), b = 16.8134(3), c = 35.9842(6) Å, and Z = 4. In these two compounds, only four pentadentate compartments are bonded to the Re 6 cluster for charge balancing. The magnetic‐susceptibility data show that there is no evidence for interactions between Fe III ions via the central Re 6 cluster in either compound. The observed effective magnetic moments suggest that there are low‐spin Fe III ions and high‐spin Fe III ions mixed in each compound. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)