| Autor: |
Aust M; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Schönherr MI; Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-Universität (LMU), Butenandtstraße 11, 81377 Munich, Germany., Halter DP; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Schröck L; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Pickl T; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Deger SN; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Hussain MZ; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Jentys A; Chair of Industrial Chemistry and Heterogeneous Catalysis, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Bühler R; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Zhang Z; Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany., Meyer K; Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstr. 1, 91058 Erlangen, Germany., Kuhl M; Walter Schottky Institute, Physics Department, TUM School of Natural Sciences, Technical University of Munich, 85747 Garching, Germany., Eichhorn J; Walter Schottky Institute, Physics Department, TUM School of Natural Sciences, Technical University of Munich, 85747 Garching, Germany., Medina DD; Department of Chemistry and Center for NanoScience (CeNS), Ludwig-Maximilians-Universität (LMU), Butenandtstraße 11, 81377 Munich, Germany., Pöthig A; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany., Fischer RA; Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, TUM School of Natural Sciences and Catalysis Research Center (CRC), Technical University of Munich, 85747 Garching, Germany. |
| Abstrakt: |
Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC 2- )─the sulfur-analog of 1,4-benzenedicarboxylate (BDC 2- )─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF) 2 ] ( 1 ) to two-dimensional (2D) honeycomb sheets observed for [Zn 2 (BDDTC) 3 ][Zn(DMF) 5 (H 2 O)] ( 2 ). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe 2 (BDDTC) 2 (OH)] ( 3 ). 3 contains a 1:1 ratio of Fe 2+/3+ ions, as evidenced by 57 Fe Mössbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2 , the Fe 2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10 -3 S cm -1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal-ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials. |
