New Si-O-P-N compounds and materials: Syntheses, structures and material properties

基于我们在DFG项目“四倍与六倍：硅酸磷配位”中有趣的结果，该项目包括Si-O-P-C/N化合物的合成以及氮对这些结构中硅配位的影响的研究。根据硅反应物的选择和反应条件，使用设想的多功能氨基膦酸将导致合成具有硅烷结构的分子模型化合物以及合成低聚物和聚合物材料。预期目标材料的质子导电性，以及导致导电性的质子定位的问题-在OH或NH基团-需要研究。除了溶剂基合成路线，热反应也将被使用。此外，膦酸与四卤化硅的反应，到目前为止已经产生了非常有趣的产物，包括[(SiL6)4+][X4]4-“盐”，将通过改变反应物而扩大。产品的表征将集中在溶液和固态核磁共振光谱上。除了反应示踪外，还将使用各种1D和2D固态核磁共振方法。直接激发和交叉极化实验用于检测、量化和表征结构基团。通过异核和同核相关实验（HETCOR， RFDR或BABA）和REDOR（旋转回声双共振）测量分析结构元素之间的邻域和联系。为了提高实验对氮的预测能力，将进行15n标记氨基膦酸的合成。这对于质子的定位（OH和NH）来说是特别有趣的。重点继续放在选定的材料属性上。除了研究Si-O-P-(C，N)-材料的热行为外，还将分析其水解阻力。由于聚合物产物可以分层沉积在不同的基底上，因此必须对其进行更详细的形态学分析。本项目基于我们获得的Si-O-P层结构和文献中描述的质子导电Zr-O-P-N化合物，采用阻抗谱法研究离子电导率。

Based on our interesting results in the DFG project "Fourfold vs. sixfold: coordination in phosphosilicates", this project includes the synthesis of Si-O-P-C/N compounds as well as the investigation of the influence of nitrogen on coordination of silicon in these structures. Depending on the choice of silicon reactants and reaction conditions, the use of the envisaged multifunctional aminophosphonic acids will lead to the synthesis of molecular model compounds with silatran structures as well as to the synthesis of oligomeric and polymeric materials. Proton conductivity is expected for the targeted materials, and the question of where the protons leading to conductivity are localized - in OH or NH groups - needs to be investigated. In addition to solvent-based synthesis routes, thermal reactions will also be used.In addition is planned that the reactions of phosphinic acids with silicon tetrahalogenides, which have so far led to very interesting products, including [(SiL6)4+][X4]4-"salts", will be expanded by varying the reactants.Characterization of the products will focus on solution and solid-state NMR spectroscopy. In addition to reaction tracings, various 1D and 2D solid-state NMR methods will be used. Direct excitation and cross-polarization experiments are used to detect, quantify and characterize the structural groups. Neighborhoods and links between structural elements are analyzed with hetero- and homonuclear correlation experiments (HETCOR, RFDR or BABA) and via REDOR (Rotational-Echo Double-Resonance) measurements. To improve the predictive power of the experiments with respect to nitrogen, the synthesis of 15N-labeled aminophosphonic acids will be performed. This is of particular interest with respect to the localization of protons (OH versus NH).The focus continues to be on selected material properties. In addition to investigating the thermal behavior of the Si-O-P-(C,N)-materials, their hydrolytic resistance will be analyzed. Since the polymeric products can be deposited as layers on different substrates, they have to be analyzed morphologically in more detail. Based on the Si-O-P layer structures obtained by us and proton-conducting Zr-O-P-N compounds described in the literature, the ionic conductivity is to be investigated by means of impedance spectroscopy in this project.