稀土簇及稀土与过渡金属簇-有机骨架的构筑及性能研究

Metal-organic frameworks have drawn extensively attention for their potential applications. So far, the study in this area mainly focused on transition metals, the analogue chemistry of lanthanide is less developed. In addition, compared with the metal-organic open frameworks based on metal ions, those constructed from metal clusters are still scarcely. To construct novel and open cluster-organic frameworks, look for new functional materials, this project will select lanthanide oxide, copper halides as metal source, 4-(4-pyridyl) benzoic acid and 4-(3-pyridyl) benzoic acid as supporting ligands to built lanthanide and lanthanide-transition metal cluster-organic frameworks, investigate the conditions of formation and stabilization of lanthanide and transition clusters, and their effective combination with ligands. Moreover, introduce small chelating ligands, regulate the size and shape of metal clusters through “synergistic coordination”, further construct lanthanide and lanthanide-transition cluster-organic open frameworks, study the structures and performances of the cluster-organic frameworks, investi- gate their absorption and ion exchange properties. This project will develop cluster chemistry, structure chemistry and coordination chemistry, possess important scientific significance.

金属-有机骨架因在吸附、分离等方面具有潜在应用而引起人们的广泛关注。目前，金属-有机骨架的研究主要集中在过渡金属，而稀土-有机骨架的研究相对较少。此外，与含金属离子的有机骨架比较，基于簇单元构筑的簇-有机骨架研究更少。为了构筑新颖、空旷的簇-有机骨架，寻找新型的功能材料，本项目将在前期工作基础上，以稀土氧化物和卤化(亚)铜为金属源，4-(4-吡啶基)苯甲酸及4-(3-吡啶基)苯甲酸为有机配体，在水热条件下合成稀土簇及稀土与过渡金属簇-有机骨架，考察稀土簇和过渡金属簇的形成、稳定及与配体有效结合并构筑簇-有机骨架的条件。此外，引入小尺寸螯合配体，通过“协同配位”来调控金属簇的尺寸及形状从而构建较空旷的稀土簇及稀土与过渡金属簇-有机骨架，研究其结构和性能，并对簇-有机空旷骨架进行吸附及离子交换等性能研究。本项目将推动原子簇化学、结构化学及配位化学的发展，具有重要的科学意义。

项目执行三年以来，我们按照研究计划，重点开展了基于稀土簇及稀土与过渡金属簇-有机骨架的构筑及性能研究，在诱导聚集和“协同配位”策略思想的指导下，采用具有课题组特色的合成策略，以稀土氧化物和卤化(亚)铜为金属源，4-(4-吡啶基)苯甲酸及4-(3-吡啶基)苯甲酸为有机配体，成功获得了一系列基于稀土团簇、稀土轮簇和稀土四面体笼的簇有机骨架，并对这些材料的物理性能进行了详细的表征，了解了卤素离子的尺寸对结构的对称性及性能也有者重要的影响，并系统研究了第二配体在该体系下的协同配位作用：轴向的主配体通常作为柱子桥连稀土簇层和过渡金属簇，而第二配体往往在赤道位辅助主配体配位。三年内在国内外学术刊物上发表影响因子大于5.0 的论文4篇，实现了项目目标。