The study of nanoporous cubic crystals derived from phthalocyanine.

我们已经发现酞菁的简单衍生物（2，3，9，10，16，17，23，24-八（2 ′，6 ′-二异丙基苯氧基）酞菁）形成立方晶体，其包含8 nm 3体积的相互连接的溶剂填充的空隙。空隙由六个酞菁以立方体排列限定，其中大环的金属离子嵌入在立方体的每个面的中心。晶体结构允许小分子（即溶剂和配体）不受阻碍地进入整个晶体，使得其充当纳米多孔材料，并且可以对金属阳离子处的配位化学进行精细控制。拟议的研究方案涉及实现该系统在多相催化中的潜力，以进行与环境相关的仿生反应;特别是氧化，脱氯反应和CO2水合。使用轴向配体来模拟在酶的活性位点处发现的“近端”配体的可能性可以允许增强系统的反应性和选择性。为了测试各种立方结构的潜力，将用金属阳离子的系统变化（包括溶剂和邻近配体）进行标准氧化和脱氯反应。我们还将评估含锌晶体的碳酸酐酶样活性，用于与封存技术相关的CO2水合。

We have discovered that a simple derivative of phthalocyanine (2,3,9,10,16,17,23,24-octa(2',6'-di-iso-propylphenoxy)phthalocyanine) forms cubic crystals which contain interconnected, solvent-filled voids of 8 nm3 volume. The voids are defined by six phthalocyanines in a cubic arrangement with the metal ion of the macrocycle embedded at the centre of each face of the cube. The crystal structure allows unhindered access of small molecules (i.e. solvent and ligands) throughout the crystal so that it acts as a nanoporous material and it is possible to exert fine control over the coordination chemistry at the metal cations. The proposed programme of research involves realising the potential of this system in heterogeneous catalysis to perform biomimetic reactions of environmental relevance; in particular oxidation, dechlorination reactions and CO2 hydration. The possibility of using axial ligands to mimic the 'proximal' ligands found at the active site of enzymes may allow the reactivity and selectivity of the system to be enhanced. To test the potential of the various cubic structures, standard oxidation and dechlorination reactions will be carried out with systematic variations of metal cation, included solvent and proximal ligand. We will also assess the carbonic anhydrase-like activity of the zinc-containing crystals for the hydration of CO2 which is of relevance to sequestration technology.