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We report the synthesis, crystal structures and magnetic properties of the giant heterometallic [Mn 36 Ni 4 ] 2−/0  (compounds  1 ,  2 )/[Mn 32 Co 8 ] (compound  3 ) “loops-of-loops-and-supertetrahedra” molecular aggregates and of a [Mn 2 Ni 6 ] 2+  compound (cation of  4 ) that is structurally related with the cation co-crystallizing with the anion of  1 . In particular, after the initial preparation and characterization of compound [Mn 2 Ni 6 (μ 4 -O) 2 (μ 3 -OH) 3 (μ 3 -Cl) 3 (O 2 CCH 3 ) 6 (py) 8 ] 2+ [Mn 36 Ni 4 (μ 4 -O) 8 (μ 3 -O) 4 (μ 3 -Cl) 8 Cl 4 (O 2 CCH 3 ) 26 (pd) 24 (py) 4 ] 2−  ( 1 ) we targeted the isolation of (i) both the cationic and the anionic aggregates of  1  in a discrete form and (ii) the Mn/Co analog of [Mn 36 Ni 4 ] 2−  aggregate. Our synthetic efforts toward these directions afforded the discrete [Mn 36 Ni 4 ] “loops-of-loops-and-supertetrahedra” aggregate [Mn 36 Ni 4 (μ 4 -O) 8 (μ 3 -O) 4 (μ 3 -Cl) 8 Cl 2 (O 2 CCH 3 ) 26 (pd) 24 (py) 4 (H 2 O) 2 ] ( 2 ), the heterometallic Mn/Co analog [Mn 32 Co 8 (μ 4 -O) 8 (μ 3 -O) 4 (μ 3 -Cl) 8 Cl 2 (μ 2 -OCH 2 CH 3 ) 2 (O 2 CCH 3 ) 28 (pd) 22 (py) 6 ] ( 3 ) and the discrete [Mn 2 Ni 6 ] 2+  cation [Mn 2 Ni 6 (μ 4 -O) 2 (μ 3 -OH) 4 (μ 3 -Cl) 2 (O 2 CCH 3 ) 6 (py) 8 ](ClO 4 )(OH) ( 4 ). The structure of  1  consists of a mixed valence [Mn    28    IIIMn    8    IINi    4    II] 2−  molecular aggregate that contains twoMn    8    IIINi    2    IIloops separated by twoMn    6    IIIMn    4    IIsupertetrahedral units and a [Mn    2    IIINi    6    II] 2+  cation based on two [Mn IIINi    3    II(μ 4 -O)(μ 3 -OH) 1.5 (μ 3 -Cl) 1.5 ] 4+  cubane sub-units connected through both mono- and tri-atomic bridges provided by the μ 4 -O 2−  and carboxylate anions. The structures of  2 – 4  are related to those of the compounds co-crystallized in  1  exhibiting however some differences that shall be discussed in detail in the manuscript. Magnetism studies revealed the presence of dominant ferromagnetic interactions in  1 – 3  that lead to large ground state spin (S T ) values for the “loops-of-loops-and-supertetrahedra” aggregates and antiferromagnetic exchange interactions in  4  that lead to a low (and possibly zero) S T  value. In particular, dc and ac magnetic susceptibility studies revealed that the discrete [Mn 36 Ni 4 ] aggregate exhibits a large S T  value ~ 26 but is not a new SMM. The ac magnetic susceptibility studies of the [Mn 32 Co 8 ] analog revealed an extremely weak beginning of an out-of-phase tail indicating the presence of a very small relaxation barrier assignable to the anisotropic Co 2+ ions and a resulting out-of-phase ac signal whose peak is at very low T.

Giant Heterometallic [Mn36Ni4]0/2− and [Mn32Co8] “Loops-of-Loops-and-Supertetrahedra” Molecular Aggregates