Magnetic behavior in heterometallic one-dimensional chains or octanuclear complex regularly aligned with metal–metal bonds as –Rh–Rh–Pt–Cu–Pt

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Heterometallic one-dimensional chains, [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}]n(PF6)2n (1 and 2, piam = pivalamidate) and [{Rh2(O2CCH3)4}{Pt2Cu(piam)4(NH3)4}2](CF3CO2)2(ClO4)2·2H2O (3), are paramagnetic one-dimensional chains or octanuclear complexes that are either aligned as –Rh–Rh–Pt–Cu–Pt– (1 and 2) or as Pt–Cu–Pt–Rh–Rh–Pt–Cu–Pt (3) with metal–metal bonds. Compounds 1–3 have rare structures, from the standpoint of that the paramagnetic species of Cu atoms are linked by direct metal–metal bonds. Magnetic susceptibility measurements for 1–3 performed at temperatures of 2 K–300 K indicated that the unpaired electrons localize in the Cu 3dx2−y2 orbitals, where S = 1/2 Cu(II) atoms are weakly antiferromagnetically coupled with J = −0.35 cm−1 (1), −0.47 cm−1 (2), and −0.45 cm−1 (3).