Abstract
A heterometallic and paramagnetic one-dimensional (1-D) chain (3) aligned as -Rh(+2)-Rh(+2)-Pt(+2)-Co(+2)-Pt(+2)- with direct metal-metal bonds was obtained by HOMO-LUMO interactions at the σ* (dz2) orbital between two kinds of complexes. The 1-D chains in 3 have relatively straight backbones because the raw material complexes, [Rh2(O2CCH3)4] and [Pt2Co(piam)4(NH3)4], are connected and stacked in a face-to-face fashion, where Co---Co are separated by about 13.3 Å with four different metals. Physical measurements revealed that 3 has a band gap between the σ-type conduction and valence bands, where d-orbitals of the Co ion with three unpaired electrons are laid among them. The magnetic behavior of 3 was investigated and found to be consistent with a complex interaction involving both zero-field splitting and Pauli paramagnetism attributed to band formation superimposed on relatively strong exchange coupling (zJ = -22.2 cm-1) between two high-spin Co(+2) ions separated by the diamagnetic Pt-Rh-Rh-Pt.
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