Die Chemie der Koordinationspolymere hat sich in den vergangenen Jahren rasant entwickelt. Strukturen aus einer Vielzahl molekularer Bausteine mit unterschiedlichen Wechselwirkungen sind mittlerweile zugänglich. Die nächste Stufe ist die chemische und physikalische Funktionalisierung dieser Architekturen durch Einstellung ihrer Porositäten. Dieser Aufsatz konzentriert sich auf drei Aspekte von Koordinationspolymeren: 1) Anwendung von Kristall‐Engineering zum Aufbau poröser Gerüste aus Konnektoren und Linkern (“Nanospace‐Engineering”), 2) Charakterisierung und Katalogisierung porös‐struktureller Funktionalität für Anwendungen in Speicherungs‐, Austausch‐, Trennprozessen etc. und 3) porös‐strukturelle Funktionalität auf der Basis dynamischer Kristallumwandlungen durch Gastmoleküle oder physikalische Reize. Ziel ist es, den aktuellen Stand der Forschung zur Chemie und Physik von und in den Mikroporen poröser Koordinationspolymere vorzustellen.

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Immobilization of coordinatively unsaturated metal centers (UMCs) into porous frameworks is a very attractive area of research because the porous framework can induce regioselectivity or shape/size selectivity by creating an appropriate environment around the metal center in the restricted available space. Furthermore, porous frameworks can stabilize the catalytic center by efficiently isolating the sites in a manner similar to the peptide architecture of enzymes in biological systems. Immobilization of UMCs into porous hosts has been attempted with zeolites, polymeric matrices, and clays through ion exchange, impregnation, and isomorphous substitution. [1,2] However, in these cases, the isolation and uniformity of the UMCs is not sufficient and the environment around the UMCs is not clear. Completely isolated and uniform catalytic centers can be realized if the UMCs are directly incorporated into channel walls of crystalline microporous coordination polymers constructed from transition-metal ions and organic bridging ligands. [3,4] Such a situation would lead to novel highly selective catalysts and sensors.In spite of the importance, the incorporation of UMCs into porous frameworks is still rare because of difficulties associated with the formation of UMCs in channel walls by a self-assembly process.[5-7] Therefore, we focused on the establishment of a rational synthetic method to immobilize various UMCs in the pore walls of microporous coordination polymers. Ligands based on metallo Schiff bases are known to be useful for the generation of supramolecular systems for homogeneous catalyses and so might be suitable for incorporation into infinite porous frameworks for applications in heterogeneous catalyses and sensors. [8,9] Here, we report a novel three-dimensional (3D) microporous coordination framework obtained from Schiff base type ligands prepared from the reaction of N,N'-phenylenebis (salicylideneimine)