Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, D-24118 Kiel, Germany.
Inorg Chem. 2013 Feb 18;52(4):1854-9. doi: 10.1021/ic301961q. Epub 2013 Jan 28.
Based on the V-shaped linker molecule 4,4'-benzophenonedicarboxylic acid, the new carbonyl-functionalized metal-organic framework (MOF) [Al(OH)(O(2)C-C(6)H(4)-CO-C(6)H(4)-CO(2))], denoted as CAU-8, was discovered employing high-throughput methods. The compound is obtained from 4,4'-benzophenonedicarboxylic acid, Al(2)(SO(4))(3)·18H(2)O in a mixture of N,N-dimethylformamide (DMF) and water under solvothermal conditions. The structure was determined from single-crystal X-ray diffraction data (I4(1)/a, a = b = 13.0625(5), c = 52.565(2) Å). The framework is based on infinite inorganic building units of trans-connected, corner-sharing AlO(6)-polyhedra. Parallel Al-O-chains are arranged in layers perpendicular to [001]. Within a layer an interchain distance of ∼1.1 nm is observed. The orientation of the Al-O-chains within neighboring layers is perpendicular to each other, along [100] and [010], respectively, and an ABCDA stacking of these layers is observed. The interconnection of these orthogonally oriented chains by the V-shaped dicarboxylate ions results in the formation a three-dimensional framework structure containing one-dimensional channels with a diameter of about 8 Å. The pore walls are lined by the keto-groups. CAU-8 was thoroughly characterized by X-ray powder diffraction (XRPD), thermogravimetric measurements, IR- and Raman-spectroscopy, elemental analysis, and gas sorption experiments using N(2) and H(2) as adsorptives. CAU-8 is stable up to 350 °C in air and exhibits a moderate porosity with a specific surface area of S(BET) = 600 m(2)/g and a micropore volume of 0.23 cm(3)/g. Moreover, a detailed topological analysis of the framework was carried out, and an approach for the topological analysis of MOFs based on infinite 1-periodic building units is proposed.
基于 V 形连接分子 4,4'- 二苯甲酮二甲酸，通过高通量方法发现了新的羰基功能化金属有机骨架（MOF）[Al(OH)(O(2)C-C(6)H(4)-CO-C(6)H(4)-CO(2))]，表示为 CAU-8。该化合物是由 4,4'- 二苯甲酮二甲酸和 Al(2)(SO(4))(3)·18H(2)O 在 N,N-二甲基甲酰胺（DMF）和水的混合物中，在溶剂热条件下得到的。通过单晶 X 射线衍射数据（I4(1)/a，a = b = 13.0625(5)，c = 52.565(2) Å）确定了结构。该骨架基于无限的无机连接单元，由交错连接的角共享 AlO(6)- 多面体组成。平行的 Al-O-链在垂直于 [001] 的层中排列。在层内观察到约 1.1nm 的链间距离。相邻层中 Al-O-链的取向彼此垂直，分别沿 [100] 和 [010]，观察到这些层的 ABCDA 堆叠。这些正交定向链通过 V 形二羧酸离子的连接导致形成具有约 8Å 直径的一维通道的三维骨架结构。孔壁由酮基基团组成。通过 X 射线粉末衍射（XRPD）、热重测量、IR 和拉曼光谱、元素分析以及使用 N(2)和 H(2)作为吸附剂的气体吸附实验，对 CAU-8 进行了彻底的表征。CAU-8 在空气中稳定至 350°C，具有中等的孔隙率，比表面积为 S(BET)=600m(2)/g，微孔体积为 0.23cm(3)/g。此外，对骨架进行了详细的拓扑分析，并提出了一种基于无限 1-周期构建单元的 MOF 拓扑分析方法。
