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  • The solid solutions (Per)(2)[PtxAu(1-x)(mnt)(2)]; alloying para-and diamagnetic anions in two-chain compounds
    Publication . Matos, Manuel; Bonfait, Gregoire; Santos, Isabel C.; Afonso, Monica L.; Henriques, Rui T.; Almeida, Manuel
    The alpha-(Per)(2)[M(mnt)(2)] compounds with M = Pt and Au are isostructural two-chain solids that in addition to partially oxidized conducting perylene chains also contain anionic chains that can be either paramagnetic in the case of M = Pt or diamagnetic for M = Au. The electrical transport and magnetic properties of the solid solutions (Per)(2)[Pt-x-Au(1-x)(mnt)(2)] were investigated. The incorporation of paramagnetic [Pt(mnt)(2)] impurities in the diamagnetic chains, and the effect of breaking the paramagnetic chains with diamagnetic centers for the low and high Pt range of concentrations were respectively probed. In the low Pt concentration range, there is a fast decrease of the metal-to-insulator transition from 12.4 K in the pure Au compound to 9.7 K for x = 0.1 comparable to the 8.1 K in the pure Pt compound. In the range x = 0.5-0.95, only beta-phase crystals could be obtained. The spin-Peierls transition of the pure Pt compound, simultaneous with metal-to-insulator (Peierls) transition is still present for 2% of diamagnetic impurities (x = 0.98) with transition temperature barely affected. Single crystal X-ray diffraction data obtained a high-quality structural refinement of the alpha- phase of the Au and Pt compounds. The beta-phase structure was found to be composed of ordered layers with segregated donors and anion stacks, which alternate with disordered layers. The semiconducting properties of the beta-phase are due to the disorder localization effects.
  • Growth of (Perylene)(2) [PD(MNT)(2)] crystals
    Publication . Afonso, M. L.; Silva, R. A. L.; Matos, Manuel; Lopes, E. B.; Coutinho, J. T.; Pereira, L. C. J.; Henriques, R. T.; Almeida, M.
    The conditions for [pd(mnt)(2)]he growth of [pd(mnt)(2)]Perylene) [pd(mnt)(2)] [Pd(mnt) [pd(mnt)(2)]] crystals either by chemical oxidation and electrochemical routes are [pd(mnt)(2)]escribed. The electrocrystallisation is limited by close [pd(mnt)(2)]roximity of [pd(mnt)(2)]he oxidation [pd(mnt)(2)]otentials of [pd(mnt)(2)]he [pd(mnt)(2)]erylene [pd(mnt)(2)]onor and [Pd(mnt) [pd(mnt)(2)]] - anion, and [pd(mnt)(2)]epending on [pd(mnt)(2)]he experimental conditions [pd(mnt)(2)]ifferent [pd(mnt)(2)]orphologies can be obtained. [pd(mnt)(2)]Per) [pd(mnt)(2)] [Pd(mnt) [pd(mnt)(2)]] crystals obtained by elecrocrystallisation were found [pd(mnt)(2)]o be [pd(mnt)(2)]ainly of [pd(mnt)(2)]he β-polymorph with [pd(mnt)(2)]roperties comparable [pd(mnt)(2)]o [pd(mnt)(2)]he Cu, Ni and Pt analogues [pd(mnt)(2)]reviously [pd(mnt)(2)]escribed at variance with [pd(mnt)(2)]hose obtained by chemical oxidation which are [pd(mnt)(2)]ainly of [pd(mnt)(2)]he α-polymorph.