Two new polynuclear d-metal clusters based on pentaerythritol (H4L), [Mn12] (1) and [Mn10Cd2] (2) for short, were obtained from the reaction of H4L, transition-metal salt and pivalic acid (Hpiv) in the mixed solvent under ambient conditions. Compound 1 crystallizes in the triclinic space group P1¯, and consists of a dodecanuclear mixed-valent [MnIII4MnII8] cluster. When Cd(NO3)2·4H2O was introduced into the reaction, compound 2 was resulted in, which displays the similar structural feature as compound 1, fabricating a dodecanuclear heterometallic [MnIII4MnII6CdII2] cluster, but crystallizes in the monoclinic space group P21/c. Interestingly, there are two μ5-O bridges present in this structure, and it is rare. Magnetic susceptibilities of compounds 1 and 2 were measured, and antiferromagnetic interactions between metal centers were observed.
