Stabilization of gold-halogen heteropolycations with borosulfate anions

计划中的研究项目的目的是稳定含硼硫酸盐阴离子的杂多阳离子。杂多阳离子应始终由金和卤素组成，因此金的氧化态可以从+1到+3变化。实验工作的起点是合成[Au3Cl4][B(S2O7)2]和[Au2Cl4][B(S2O7)2](SO3)。通过在SO3中的强氧化条件下工作，已经可以制备上述化合物。它们被双二硫硼酸根阴离子稳定，这可以被认为是弱配位阴离子。这些阴离子优先在这些极端条件下形成，也将用于计划研究项目的大多数化合物的阳离子亚结构的电荷补偿。类似于合成[Au3Cl4][B(S2O7)2]和[Au2Cl4][B(S2O7)2](SO3)，硼酸将与AuCl2、AuCl2和AuCl3在SO3中反应生成更多的Au-Cl杂多阳离子。除了化学计量组成的变化外，还将研究温度对溶剂热反应过程中产物形成的影响。随后，将使用溴化金、碘化物和氟化物作为起始原料。预计AuBr3和AuBr3的反应产物将形成类似于氯化物的结构。由于碘阴离子明显较大而氟化物显著较小，因此所得产物应具有不同的阳离子亚结构。对于含有Au2+的化合物，应尝试用等价阳离子Pd2+或Hg2+取代。[Au_2Cl4][B(S_2O_7)_2](SO_3)是一种由Au~(2+)和Au~(3+)离子组成的波状平面配位金属，是一维金属。因此，在通过单晶和粉末X射线衍射、红外光谱和拉曼光谱以及热重分析进行常规表征之后，研究项目获得的所有产品都将根据产品的结构和性质进行进一步的磁化学和导电性研究。能带结构计算支持实验结果。在磁性化学测量、电导率测量、XPS和能带结构计算方面，已经与科隆大学的同事达成了合作协议。

The aim of the planned research project is to stabilize heteropolycations with borosulfate anions. The heteropolycations should always consist of gold and a halogen, whereby the oxidation state of the gold can vary from +1 to +3. The starting point of the experimental work is the synthesis of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3). By working under strongly oxidizing conditions in SO3, it has been possible to prepare the aforementioned compounds. These are stabilized by bis-disulfatoborate anions, which can be regarded as weakly coordinating anions. These anions are preferentially formed under these extreme conditions and will also serve for charge compensation of the cationic substructure for most of the compounds of the planned research project. In analogy to the synthesis of [Au3Cl4][B(S2O7)2] and [Au2Cl4][B(S2O7)2](SO3), further Au-Cl heteropolycations will be prepared from the reaction of boric acid with AuCl, AuCl2 and AuCl3 in SO3. Besides the variation of the stoichiometric composition, the influence of temperature on the product formation during the solvothermal reactions will be studied. Subsequently, gold bromides, iodides and fluorides will be used as starting materials. It is expected that the products of the reactions of AuBr and AuBr3 will form structures similar to those found for the chlorides. Since iodide anions are significantly larger and fluoride is significantly smaller, the products obtained should have different cationic substructures. For compounds containing Au2+, substitution with the isovalent cations Pd2+ or Hg2+ should be attempted. [Au2Cl4][B(S2O7)2](SO3) exhibits a wave-like arrangement of square planar coordinated Au2+ as well as Au3+ cations and has been characterized as a one-dimensional metal. Accordingly, after a routine characterization via single crystal and powder X-ray diffraction, IR and Raman spectroscopy as well as thermogravimetry, all obtained products of the research project will be subjected to further studies regarding magnetochemistry and conductivity, depending on the structure and nature of the products. Band structure calculations support the experimental results. For magentochemical measurements, conductivity measurements, XPS and band structure calculations, cooperation agreements have been made with colleagues at the University of Cologne.