Enhanced Ion Anisotropy by Nonconventional Coordination Geometry: Single-Chain Magnet Behavior for a [{FeIIL}2{NbIV(CN)8}] Helical Chain Compound Designed with Heptacoordinate FeII

Abstract

Nonconventional heptacoordination in combination with efficient magnetic exchange coupling is shown to yield a 1-D heteronuclear {Fe(II)Nb(IV)} compound with remarkable magnetic features when compared to other Fe(II)-based single chain magnets (SCM). Cyano-bridged heterometallic {3d-4d} and {3d-5d} chains are formed upon assembling Fe(II) bearing a pentadentate macrocycle as the blocking ligand with octacyano metallates, [M(CN)(8)](4-) (M = Nb(IV), Mo(IV), W(IV)). X-ray diffraction (single-crystal and powder) measurements reveal that the [{(H(2)O)Fe(L(1))}{M(CN)(8)}{Fe(L(1))}](infinity) architectures consist of isomorphous 1-D polymeric structures based on the alternation of {Fe(L(1))}(2+) and {M(CN)(8)}(4-) units (L(1) stands for the pentadentate macrocycle). Analysis of the magnetic susceptibility behavior revealed cyano-bridged {Fe-Nb} exchange interaction to be antiferromagnetic with J = -20 cm(-1) deduced from fitting an Ising model taking into account the noncollinear spin arrangement. For this ferrimagnetic chain a slow relaxation of its magnetization is observed at low temperature revealing a SCM behavior with Delta/k(B) = 74 K and tau(0) = 4.6 x 10(-11) s. The M versus H behavior exhibits a hysteresis loop with a coercive field of 4 kOe at 1 K and reveals at 380 mK magnetic avalanche processes, i.e., abrupt reversals in magnetization as H is varied. The origin of these characteristics is attributed to the combination of efficient {Fe-Nb} exchange interaction and significant anisotropy of the {Fe(L(1))} unit. High field EPR and magnetization experiments have revealed for the parent compound [Fe(L(1))(H(2)O)(2)]Cl(2) a negative zero field splitting parameter of D approximately = -17 cm(-1). The crystal structure, magnetic behavior, and Mossbauer data for [Fe(L(1))(H(2)O)(2)]Cl(2) are also reported.