Crystal Structures and Properties of MMX-Chain Compounds Based on Dithiocarboxylato-Bridged Dinuclear Complexes
作者： Minoru Mitsumi
DOI: 10.1007/978-3-7091-1317-2_9
关键词: Peierls transition 、 Molecular dynamics 、 Crystallography 、 Metal 、 Electrical resistivity and conductivity 、 Heat capacity 、 Alkyl 、 Phase transition 、 Materials science 、 Crystal structure
摘要: In this chapter, a comprehensive study of the syntheses, crystal structures, and properties series one-dimensional (1D) halogen-bridged mixed-valence dimetal complexes, MMX-chain compounds, based on dithiocarboxylato-bridged dinuclear [Pt2(RCS2)4I]∞ (R = Me (1), Et (2), n-Pr (3), n-Bu (4), n-Pen (5), n-Hex(6)) [Ni2(RCS2)4I]∞ (7), (8), (9), (10)) are described. The evolution from 1D metal complex, MX-chain to compounds has produced variety electronic states subtle balance solid-state originating charge–spin–lattice coupling fluctuation these degrees freedom. With increasing internal freedom diplatinum unit, Pt except for 3 show relatively high electrical conductivity 0.84–43 S cm–1 at room temperature exhibit metallic conducting behavior with T M–S 205–324 K. These considered take valence-ordered state close an averaged-valence (AV) –Pt2.5+–Pt2.5+–I––. analyses diffuse scattering observed in 2 revealed that appeared by valence accompanying dynamic valence-ordering charge-density-wave (CDW) type –Pt2+–Pt2+–I––Pt3+–Pt3+–I––. On other hand, become insulators lowering due lattice dimerization effective half-filled band. synchrotron radiation structure analysis 48 K LT phase is alternate charge-polarization (ACP) –Pt2+–Pt3+–I––Pt3+–Pt2+–I––. Furthermore, elongation alkyl chains introduces motional system. Interplay between molecular dynamics also expected cause intriguing structural transition and/or magnetic never [M2(MeCS2)4I]∞ (M Ni (7)). dithiocarboxylato ligands, 3–5 undergo two transitions near 210 above temperature, indicating existence LT, RT, HT phases. periodicity RT along chain threefold –Pt–Pt–I– disorders have occurred group belonging only central units periodicity. phase, groups all disordered periodicities 4 change onefold period. Ikeuchi Saito heat capacity measurements entropy (disorder) reserved transferred dithiocarboxylate RT–HT [50–52]. Whereas, changes twofold being assigned ACP similar compound ordered. RT–LT transition, exhibits paramagnetic–nonmagnetic regular Peierls transition. facts suggest (motional freedom) ligands bridging iodine atoms affects systems through electron–lattice interaction.
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