[Fe(bpym)(CN)4]-: a new building block for designing single-chain magnets.
We herein present the preparation, crystal structure, magnetic properties, and theoretical study of new heterobimetallic chains of formula {[Fe(III)(bpym)(CN4)]2M(II)(H2O)2}.6H2O [bpym = 2,2'-bipyrimidine; M = Zn (2), Co (3), Cu (4), and Mn (5)] which are obtained by using the building block PPh4[Fe(bpym)(CN)4].H2O (1) (PPh4+= tetraphenylphosphonium) as a ligand toward the fully solvated MII ions. The structure of complex 1 contains mononuclear [Fe(bpym)(CN)4]- anions. Compounds 2-5 are isostructural 4,2-ribbonlike bimetallic chains where the [Fe(bpym)(CN)4]- unit acts as a bis-monodenate ligand through two of its four cyanide ligands toward the M atom. Water hexamer clusters (4) and regular alternating fused six- and four-membered water rings with two dangling water molecules (2, 3, and 5) are trapped between the cyanide-bridged 4,2-ribbonlike chains. 1 and 2 behave as magnetically isolated low-spin iron(III) centers. 3 behaves as a single-chain magnet (SCM) with intrachain ferromagnetic coupling, slow magnetic relaxation, hysteresis effects, and frequency-dependent ac signals at T < 7 K). As expected for a thermally activated process, the nucleation field (Hn) in 3 increases with decreasing T and increasing v. Below 1.0 K, Hn becomes temperature independent but remains strongly sweep rate dependent. In this temperature range, the reversal of the magnetization may be induced by a quantum nucleation of a domain wall that then propagates due to the applied field. 4 and 5 are ferro- and ferrimagnetic chains respectively, with metamagnetic-like behavior (4). DFT-type calculations and QMC methodology provided a good understanding of the magnetic properties of 3-5.
Toma
Luminita Marilena
LM
Departament de Química Inorganica/Instituto de Ciencia Molecular, Facultat de Química de la Universitat de València, Avda. Dr. Moliner 50, 46100 Burjassot, València, Spain.
Lescouëzec
Rodrigue
R
Pasan
Jorge
J
Ruiz-Pérez
Catalina
C
Vaissermann
Jacqueline
J
Cano
Joan
J
Carrasco
Rosa
R
Wernsdorfer
Wolfgang
W
Lloret
Francesc
F
Julve
Miguel
M