The inclusion of Ln(III) ions into the 12-MC-4 framework generates the first heterotrimetallic complexes of this molecular class. The controllable and deliberate preparations of these compounds are demonstrated through 12 crystal structures of the Ln(III)M(I)(OAc)4[12-MCMn(III)(N)shi-4](H2O)4·6DMF complex, where OAc(-) is acetate, shi(3-) is salicylhydroximate, and DMF is N,N-dimethylformamide. Compounds 1-12 have M(I) as Na(I), and Ln(III) can be Pr(III) (1), Nd(III) (2), Sm(III) (3), Eu(III) (4), Gd(III) (5), Tb(III) (6), Dy(III) (7), Ho(III) (8), Er(III) (9), Tm(III) (10), Yb(III) (11), and Y(III) (12). An example with M(I) = K(I) and Ln(III) = Dy(III) is also reported (Dy(III)K(OAc)4[12-MCMn(III)(N)shi-4](DMF)4·DMF (14)). When La(III), Ce(III), or Lu(III) is used as the Ln(III) ions to prepare the Ln(III)Na(I)(OAc)4[12-MCMn(III)(N)shi-4] complex, the compound Na2(OAc)2[12-MCMn(III)(N)shi-4](DMF)6·2DMF·1.60H2O (13) results. For compounds 1-12, the identity of the Ln(III) ion affects the 12-MCMn(III)(N)shi-4 framework as the largest Ln(III), Pr(III), causes an expansion of the 12-MCMn(III)(N)shi-4 framework as demonstrated by the largest metallacrown cavity radius (0.58 Å for 1 to 0.54 Å for 11), and the Pr(III) causes the 12-MCMn(III)(N)shi-4 framework to be the most domed structure as evident in the largest average angle about the axial coordination of the ring Mn(III) ions (103.95° for 1 to 101.69° for 11). For 14, the substitution of K(I) for Na(I) does not significantly affect the 12-MCMn(III)(N)shi-4 framework as many of the structural parameters such as the metallacrown cavity radius (0.56 Å) fall within the range of compounds 1-12. However, the use of the larger K(I) ion does cause the 12-MCMn(III)(N)shi-4 framework to become more planar as evident in a smaller average angle about the axial coordination of the ring Mn(III) ions (101.35°) compared to the analogous Dy(III)/Na(I) (7) complex (102.40°). In addition to broadening the range of structures available through the metallacrown analogy, these complexes allow for the mixing and matching of a diverse range of metals that might permit the fine-tuning of molecular properties where one day they may be exploited as magnetic materials or luminescent agents.

A family of DyXM(12-MC-4) compounds were synthesized and magnetically characterized (X = salicylate, acetate, benzoate, trimethylacetate, M = Na or K). The bridging ligands were systematically varied while keeping the remainder of the MC-geometry constant. The type of monovalent cation, necessary for charge balance, was also altered. The dc magnetization and susceptibility of all compounds were similar across the series. Regardless of the identity of the countercation, the Dy(Hsal)M 12-MC-4 compounds were the only compounds to show frequency-dependent ac magnetic susceptibility, a hallmark of single-molecule magnetism. This indicates that the nature of the bridging ligand in the 12-MC-4 compounds strongly affects the out-of-phase magnetic properties. The SMM behavior appears to correlate with the pK of the bridging ligand.

We describe the syntheses of a series of sodium aminodiboranate salts, Na(H 3 B−NR 2 −BH 3 ), with different substituents on nitrogen, including sodium salts of the unsubstituted aminodiboranate, H 3 B−NH 2 −BH 3 − , and of the N-substituted anions H 3 B−NRR′−BH 3 − , where NRR′ = NHMe, NHEt, NH(SiMe 3 ), NEt 2 , N(i-Pr) 2 , N(SiMe 3 ) 2 , NMe(i-Pr), NMe(t-Bu), NMe-(SiMe 3 ), and the pyrrolidide and piperidide derivatives NC 4 H 8 , NC 5 H 10 , and NC 5 H 8 -cis-2,6-Me 2 . The compounds have been characterized by 1 H and 11 B NMR spectroscopy and IR spectroscopy; crystallographic studies have been carried out for the unsolvated N,N-dimethylaminodiboranate salt Na-(H 3 B−NMe 2 −BH 3 ) and several sodium aminodiboranate salts in which the sodium ions are solvated with ethers (dioxane, diglyme, tetrahydrofuran, and 12-crown-4) or amines (N,N,N′,N′tetramethylethylenediamine). One of the structures contains a rare example of an ether ligand in which one oxygen atom bridges between two metal ions. General structural and spectroscopic trends as a function of the substituents on nitrogen are discussed.

The title compound consists of a macrocyclic ring with an MnIII—N—O repeat unit that occurs four times, producing a mol­ecule with an overall square structure. Two Na+ ions are captured above and below the central cavity of the mol­ecule.