The electrochemical oxidation of an acetone solution or acetonitrile (MeCN) solution containing [MnIII2 (5 -MeOsaltmen)2 (H2 O)2](PF6)2 (5-MeOsaltmen2- = N,N′-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu4)[Ni(dmit)2] (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) has yielded two unique hybrid materials in which [Mn2]2+ single-molecule magnets (SMMs) possessing an ST = 4 ground state and [Ni(dmit)2]n- molecules each possessing an average valence of ca.-0.29 are aggregated in a layer-by-layer form; [Mn2(5-MeOsaltmen)2(acetone)2][Ni(dmit)2]7 · 4acetone (1) and [Mn2(5-MeOsaltmen)2(MeCN)2][Ni(dmit)2]7 · 4MeCN (2).Compounds 1 and 2 have a similar structure to each other and crystallize in the triclinic P over(1, ̄) space group with inversion centers on the midpoint of Mn⋯Mn vector of the dimer and a Ni ion of one of [Ni(dmit)2]0.29- molecules (i.e., Z = 1).The [Mn2]2+ unit has a typical Mn(III) out-of-plane dimeric core and is structurally consistent with the already reported [Mn2] SMMs.Seven [Ni(dmit)2]0.29- units in the formula have a square-planar coordination geometry in common, and the charge distribution among them can be averagely assigned according to their local structures and IR spectra; thus, the formal charge for each molecule is -0.29.These two kinds of molecules,[Mn2]2+ SMM units and [Ni(dmit)2]0.29- units, construct hybrid frames aggregating individually, where the latter units form a β-type stacking arrangement. Electronic conductivity measurements revealed that 1 and 2 are semiconductors with σrt = 1.6 S cm-1 and 2.8 S cm-1, respectively, at room temperature. The detail magnetic measurements proved that the [Mn2]2+ units in 1 and 2 behave as ST = 4 SMMs at low temperatures, although their conductivities are already insulated at such temperatures.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry