The linear trirhodium compound, Rh3(dpa)4Cl2 (1), and its one-electron oxidation product, [Rh3(dpa)4Cl2]BF4 (2), have been synthesized and studied extensively. The magnetic measurement for compound 1 shows that it possesses one unpaired electron that is assigned to occupy the σnb orbital (2A2) by DFT calculations. Upon oxidation, a β-spin electron of 1 is removed, that causes compound 2 to exhibit a triplet ground state. DFT calculations indicate that the two unpaired electrons of 2 occupy σnb and δ* orbitals (3B1), which is supported by 1H NMR spectrum. Unlike their isoelectronic analogues [Co3(dpa)4Cl2] (3) and [Co3(dpa)4(Cl)2]BF4 (4), both compound 1 and 2 do not display the spin-crossover phenomenon. The reason may be attributed to the relative large energy gap between 3B1 and open-shell singlet 1B1 states.
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