Metastable Crystalline Metal Imidazolates; Development of Targeted Syntheses by Combining Experimental and Theoretical Investigations of the Formation Mechanisms

由于第一期取得的进展，第二期的工作将集中于亚稳结晶咪唑酸锌（“沸石咪唑酸框架”）。第二阶段的目标是开发具有4,5-二取代咪唑酸桥接配体的新型亚稳ZlFs的靶向合成。合成的一个特别的、新颖的方面应该是使用简单的单配体，在成核（和晶体生长）过程中，作为锌阳离子络合物形成平衡和咪唑衍生物去质子平衡的调制剂，从而能够选择形成的相。为了合成的发展，对分子和胶体形成过程的详细机理的理解应该通过广泛的实验时间分辨的非原位和原位研究来实现，通过应用动力学模型来解释获得的时间依赖的散射数据，以及在明确考虑溶剂和调节剂分子的情况下对成核过程进行理论建模。新的，潜在存在的zif作为可能的合成目标，应通过理论方法与拓扑数据库进行预测。

Owing to the progress made in the first period the work for the second period shall concentrate on metastable crystalline zinc imidazalotes ("Zeolitic Imidazolate Frameworks", ZIFs). The aim of the second period shall be the development of targeted syntheses of new metastable ZlFs with 4,5-disubstituted imidazolate bridging ligands (linkers). A particular, novel aspect of the syntheses shall be the use of simple monotopic ligands that act as modulators on the complex formation equilibria at the zinc cations and the deprotonation equilibria at the imidazole derivative during nucleation (and crystal growth), thereby enabling a selection of the phase to be formed. For synthesis development a detailed mechanistic understanding of the molecular and colloidal formation processes shall be achieved via extensive experimental time-resolved ex-situ and in-situ investigations of the reactions, interpretation of the obtained time-dependent scattering data by application of kinetic models, and theoretical modeling of the nucleation processes with explicit consideration of solvent and modulator molecules. New, potentially existing ZIFs as possible synthesis targets shall be predicted by theoretical methods with recourse to topological databases.