Synthesis of a Cu-Filled Rh17S15 Framework: Microwave Polyol Process Versus High-Temperature Route.
Synthesis of a Cu-Filled Rh17S15 Framework: Microwave Polyol Process Versus High-Temperature Route.
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DOI：
10.1021/acs.inorgchem.7b01102
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发表时间：
2017-09
影响因子：
4.6
通讯作者：
M. Roslova;Pavlo Golub;L. Opherden;A. Ovchinnikov;M. Uhlarz;A. Baranov;Y. Prots;A. Isaeva;M. Coduri;T. Herrmannsdörfer;J. Wosnitza;T. Doert;M. Ruck
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文献类型：
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作者：
M. Roslova;Pavlo Golub;L. Opherden;A. Ovchinnikov;M. Uhlarz;A. Baranov;Y. Prots;A. Isaeva;M. Coduri;T. Herrmannsdörfer;J. Wosnitza;T. Doert;M. Ruck
合成了一种新的铜填充δ结构的富金属硫化铜-Rh_3Rh_(34)S_(30)，并对其结构进行了表征。发现[CuRh8]立方簇合物中的铜含量随所选合成路线的不同而显著不同。Cu3-δRh34S30与Rh2(CH3CO2)4和氨基硫代氨基硫化物在300°C的快速微波辅助反应仅需30分钟即可实现全位占位；而在950°C下，通过传统的高温陶瓷合成方法仅获得了缺乏铜的Cu3-≥δ≥Rh34S30(2.0≥δ≥0.9)组分。虽然Cu3-δRh34S30和Rh17S15一样是金属的，但金属含量的略微增加对电子性质有很大的影响。然而Rh17S15的主体在5.4K经历了超导转变，而铜的衍生物没有发现超导转变的迹象，至少在1.8K以下。这一发现被量子化学计算揭示的三元硫化物费米能级的态密度显著降低和有利于铜-Rh相互作用的Rh-Rh长程相互作用的破坏所证实。
Metal-rich, mixed copper-rhodium sulfide Cu3-δRh34S30 that represents a new Cu-filled variant of the Rh17S15 structure has been synthesized and structurally characterized. Copper content in the [CuRh8] cubic cluster was found to vary notably dependent on the chosen synthetic route. Full site occupancy was achieved only in nanoscaled Cu3Rh34S30 obtained by a rapid, microwave-assisted reaction of CuCl, Rh2(CH3CO2)4 and thiosemicarbazide at 300 °C in just 30 min; whereas merely Cu-deficient Cu3-δRh34S30 (2.0 ≥ δ ≥ 0.9) compositions were realized via conventional high-temperature ceramic synthesis from the elements at 950 °C. Although Cu3-δRh34S30 is metallic just like Rh17S15, the slightly enhanced metal content has a dramatic effect on the electronic properties. Whereas the Rh17S15 host undergoes a superconducting transition at 5.4 K, no signs of the latter were found for the Cu-derivatives at least down to 1.8 K. This finding is corroborated by the strongly reduced density of states at the Fermi level of the ternary sulfide and the disruption of long-range Rh-Rh interactions in favor of Cu-Rh interactions as revealed by quantum-chemical calculations.