We report now the first single molecule magnet (SMM) consisting of d-f elements. The present study demonstrates that the synthesis of the d-f polynuclear molecule is a very promising approach to SMMs. (1) The d-f polynuclear molecule can be easily synthesized by the assembly reaction of the d-component and the f-component, (2) the high-spin ground state can be generated by a smaller number of metal ions than the d complex, and (3) the molecular magnetic anisotropy is easily derived from the f-component.
The reaction between the
[Mn(BS)(H2O)]+ monomeric and
[Mn2(μ-BS)2(H2O)2]2+
dimeric cations and
[Fe(CN)6]3- gave rise to
cation−anion interaction via the formation of
[FeC⋮NMn] bridges. Depending on the
nature of the Schiff base and regardless of the stoichiometry used,
either the trimeric anion
[{Mn(BS)}2{Fe(CN)6}]-
(BS = 3-MeOsalen, 6; 5-Clsalen, 7; 5-Brsalen,
8; salcy, 10) or the pentameric cation
[{Mn(BS)}4{Fe(CN)6}]+
(BS
= saltmen, 9) is formed, which has been assembled by the
K+ cation or the ClO4
- anion,
respectively. The X-ray
analysis of 6 revealed a two-dimensional network layer
structure. The magnetic measurements showed its
metamagnetic behavior, where the ferromagnetic interaction operates
within each layer and the antiferromagnetic
interaction operates between the layers. The Neel temperature,
T
N, is 9.2 K, and the critical field at 2 K is
300 Oe.
The temperature dependent magnetic susceptibilities of
7 and 8 are in agreement with a discrete,
symmetrical, trinuclear
structure Mn(III)Fe(III)Mn(III)
(S
Mn = 2, S
Fe = 1/2,
S
Mn = 2) with a ferromagnetic spin coupling
between the
Mn(III) and Fe(III) ions, a small antiferromagnetic
intertrimer interaction, and a large zero-field splitting of
the
Mn(III) ion. The structure of 9 consists of a
two-dimensional layer containing as the repeating unit a cyclic
dodecamer.
The layers stack along the c axis, and
ClO4
- anions are positioned between the
layers. The magnetic measurements
showed this compound's ferromagnetic behavior. There are, in
fact, two kinds of intralayer magnetic interactions,
the interaction between the Fe(III) and Mn(III) ions bridged
by CN groups and the interaction between two Mn(III)
ions in the dimer [Mn2(saltmen)2], both
being ferromagnetic. The interlayer magnetic interaction is
ferromagnetic.
All of the interactions render to 9 an overall
ferromagnetic behavior.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.