Structure, phase transition and properties of the one-dimensional antiferromagnet Cu(2,6-dimethylpyrazine)Br 2 .

We report the crystal structure and properties of the one-dimensional S = 1/2 antiferromagnet Cu(2,6-dimethylpyrazine)Br 2 with strong intra-chain exchange. At room temperature, its linear spin chains are formed by Cu 2+ ions via the non-bonding Br⋯Br contacts. Interestingly, a phase transition from Pmmn to P 21/ n structure occurs at T S ≈ 248 K below which the [CuBr 2 ] n spin chains become non-linear and the magnetic susceptibility abruptly increases, reflecting the weakening of antiferromagnetic exchange strength. This result evidences the Goodenough-Kanamori rules which claim that a linear super-exchange pathway produces stronger antiferromagnetic coupling. From magnetic susceptibility measurements we find the average intra-chain exchange strength is J / k B ≈ -88.18 K in the low temperature phase. Both magnetic and specific measurements show the absence of magnetic ordering down to 2 K, implying the excellent magnetic one-dimensionality of Cu(2,6-dimethylpyrazine)Br 2 . We also performed ultra-violet (UV) absorption and photoluminescence measurements which give a semiconducting band gap Δ ≈ 2.79 eV which is consistent with theoretical calculations.