Stabilization of gold-halogen heteropolycations with borosulfate anions

计划研究项目的目的是稳定与硼硫酸盐阴离子的杂多聚。杂多化合物应该总是由金和卤素组成，因此金的氧化态可以从+1到+3变化。实验工作的出发点是合成[Au3Cl4][B(S2O7)2]和[Au2Cl4][B(S2O7)2]（SO3）。通过在SO3的强氧化条件下工作，可以制备上述化合物。这些是稳定的双二硫代硼酸盐阴离子，可视为弱配位阴离子。这些阴离子在这些极端条件下优先形成，也将为计划研究项目中大多数化合物的阳离子子结构提供电荷补偿。与合成[Au3Cl4][B(S2O7)2]和[Au2Cl4][B(S2O7)2]（SO3）类似，硼酸在SO3中与AuCl、AuCl2和AuCl3反应，进一步制备Au-Cl杂多物。除了化学计量成分的变化外，还研究了溶剂热反应过程中温度对产物形成的影响。随后，金溴化物、碘化物和氟化物将被用作起始原料。预计AuBr和AuBr3的反应产物将形成与氯化物相似的结构。由于碘离子的阴离子要大得多，而氟离子的阴离子要小得多，因此得到的产物应该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。[Au2Cl4][B(S2O7)2]（SO3）表现出方形平面配位的Au2+和Au3+阳离子的波状排列，具有一维金属的特征。因此，在通过单晶和粉末x射线衍射，红外和拉曼光谱以及热重法进行常规表征后，根据产品的结构和性质，将对研究项目获得的所有产品进行进一步的磁化学和电导率研究。带结构计算支持实验结果。对于磁化学测量、电导率测量、XPS和能带结构计算，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.