Core–Shell {Mn7⊂(Mn,Cd)12} Assembled from Core {Mn7} Disc

Postsynthetic decoration of the Mn7, {MnIII⊂MnII6}, core with CdII in the outer shell to form the next generation Mn13Cd6, {MnIII⊂MnIII3MnII3⊂ MnII6CdII6}, core–shell disc was achieved and confirmed by single-crystal X-ray diffraction. The formation of Mn13Cd6 has only been successful with CdII and if the Cd salt is added within the first half hour window when the inner Mn7 has formed. EDX and ICP-AES gave the accurate content and confirm the average found by X-ray diffraction. HR-ESI-MS was even more precise by revealing three prominent molecular species, Mn13Cd6, Mn14Cd5 and Mn15Cd4, having a distribution of metals. The presence of nonmagnetic metal on the periphery reduces the exchange between these clusters as well as the low magnetic moment decreases the dipolar interaction resulting in a paramagnet compared to the ferrimagnetism found for the parent Mn19, {MnIII⊂MnIII3MnII3⊂MnII12}, disc. This study opens the way for the syntheses of heterometallic core–shell clusters in a controllable fashion.