Abstract
The solid state structure of (C5H4Me)2Mn is determined and its solid state magnetism investigated. (C5H4Me)2Mn is a chain polymer, as is the parent (C5H5)2Mn (Bünder W.; Weiss, E. Z. Naturforsch.1978, 33b, 1237), and they exhibit very similar solid state magnetic susceptibilities that are modeled as an antiferromagnetically-coupled linear Heisenberg-chain of high-spin Mn(II) centers (S = 5/2) (König, E.; Desai, V. P.; Kanellakopulos, B.; Klenze, R. Chem. Phys.1980, 54, 109). Doping of these manganocenes into diamagnetic hosts such as (C5H4Me)2Fe and (C5H5)2Fe, respectively, stabilizes the low-spin configuration (S = 1/2) relative to the high-spin configuration (S = 5/2). At higher temperatures the solid solutions of these manganocenes show spin-crossover behavior modeled by a Boltzmann distribution of spins to give ΔH0 ≈ 1.7 kcal mol−1 and ΔS0 ≈ 5 cal (mol K)−1 for the LS ⇌ HS equilibria.
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