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Poly-MTO, {(CH_3)_{0.92} Re O_3}_infty, a Conducting Two-Dimensional Organometallic Oxide

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 Publication date 2005
  fields Physics
and research's language is English




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Polymeric methyltrioxorhenium, {(CH_{3})_{0.92}ReO_{3}}_{infty} (poly-MTO), is the first member of a new class of organometallic hybrids which adopts the structural pattern and physical properties of classical perovskites in two dimensions (2D). We demonstrate how the electronic structure of poly-MTO can be tailored by intercalation of organic donor molecules, such as tetrathiafulvalene (TTF) or bis-(ethylendithio)-tetrathiafulvalene (BEDT-TTF), and by the inorganic acceptor SbF$_3$. Integration of donor molecules leads to a more insulating behavior of poly-MTO, whereas SbF$_3$ insertion does not cause any significant change in the resistivity. The resistivity data of pure poly-MTO is remarkably well described by a two-dimensional electron system. Below 38 K an unusual resistivity behavior, similar to that found in doped cuprates, is observed: The resistivity initially increases approximately as $rho sim$ ln$(1/T$) before it changes into a $sqrt{T}$ dependence below 2 K. As an explanation we suggest a crossover from purely two-dimensional charge-carrier diffusion within the {ReO$_2$}$_{infty}$ planes at high temperatures to three-dimensional diffusion at low temperatures in a disorder-enhanced electron-electron interaction scenario (Altshuler-Aronov correction). Furthermore, a linear positive magnetoresistance was found in the insulating regime, which is caused by spatial localization of itinerant electrons at some of the Re atoms, which formally adopt a $5d^1$ electronic configuration. X-ray diffraction, IR- and ESR-studies, temperature dependent magnetization and specific heat measurements in various magnetic fields suggest that the electronic structure of poly-MTO can safely be approximated by a purely 2D conductor.



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Polymeric methyltrioxorhenium (poly-MTO) is the first member of a new class of organometallic hybrids which adopts the structural motives and physical properties of classical perowskites in two dimensions. In this study we demonstrate how the electronic structure of poly-MTO can be tailored by intercalation of organic donor molecules such as tetrathiafulvalene (TTF). With increasing donor intercalation the metallic behavior of the parent compound, (CH$_{3}$)$_{0.92}$ReO$_{3} cdot x%$ TTF ($x = 0$) becomes suppressed leading to an insulator at donor concentrations $x$ larger than 50. Specific heat, electric resistance and magnetic susceptibility studies indicate that an increasing amount of TTF causes the itinerant electrons of the poly-MTO matrix to localize.
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