Studies of Finite Molecular Chains: Synthesis, Structural, Magnetic and Inelastic Neutron Scattering Studies of Hexa- and Heptanuclear Chromium Horseshoes

We report the synthesis and structural characterisation of a family of finite molecular chains, specifically [{[R2NH2]3[Cr6F11(O2CCMe3)10]}2] (in which R=nPr 1, Et 2, nBu 3), [{Et2NH}2{[Et2NH2]3[Cr7F12(O2CCMe3)12][HO2CCMe3]2}2] (4), [{[Me2NH2]3[Cr6F11(O2CCMe3)10]⋅2.5 H2O}4] (5) and [{[iPr2NH2]3[Cr7F12(O2CCMe3)12]}2] (6). The structures all contain horseshoes of chromium centres, with each Cr⋅⋅⋅Cr contact within the horseshoe bridged by a fluoride and two pivalates. The horseshoes are linked through hydrogen bonds to the secondary ammonium cations in the structure, leading to di‐ and tetra‐horseshoe structures. Through magnetic measurements and inelastic neutron scattering studies we have determined the exchange coupling constants in 1 and 6. In 1 it is possible to distinguish two exchange interactions, JA=−1.1 meV and JB=−1.4 meV; JA is the exchange interactions at the tips of the horseshoe and JB is the exchange within the body of the horseshoe (1 meV=8.066 cm−1). For 6 only one interaction was needed to model the data: J=−1.18 meV. The single‐ion anisotropy parameters for CrIII were also derived for the two compounds as: for 1, DCr=−0.028 meV and |ECr|=0.005 meV; for 6, DCr=−0.031 meV. Magnetic‐field‐dependent inelastic neutron scattering experiments on 1 allowed the Zeeman splitting of the first two excited states and level crossings to be observed. For the tetramer of horseshoes (5), quantum Monte Carlo calculations were used to fit the magnetic susceptibility behaviour, giving two exchange interactions within the horseshoe (−1.32 and −1.65 meV) and a weak inter‐horseshoe coupling of +0.12 meV. Multi‐frequency variable‐temperature EPR studies on 1, 2 and 6 have also been performed, allowing further characterisation of the spin Hamiltonian parameters of these chains. Magnetic horseshoes! The size and degree of aggregation of {Crn} horseshoes can be controlled by choice of secondary amines used to template the formation of the suprastructures (an example is shown here). Magnetic, inelastic neutron scattering and electron paramagnetic resonance spectroscopic studies have been used to examine how well these finite chains can be described by spin‐wave theory.