American Chemical Society
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[Fe(bpym)(CN)4]-: A New Building Block for Designing Single-Chain Magnets

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journal contribution
posted on 2006-04-12, 00:00 authored by Luminita Marilena Toma, Rodrigue Lescouëzec, Jorge Pasán, Catalina Ruiz-Pérez, Jacqueline Vaissermann, Joan Cano, Rosa Carrasco, Wolfgang Wernsdorfer, Francesc Lloret, Miguel Julve
We herein present the preparation, crystal structure, magnetic properties, and theoretical study of new heterobimetallic chains of formula {[FeIII(bpym)(CN4)]2MII(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 25 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 35.