Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) are recently developed ordered porous solids and widely known as promising materials for applications in gas storage, separation, catalysis or others. One of their key advantages compared to their organic (carbons) or inorganic counterparts (zeolites, silica), is custom-designed porous structures with their properties tuned through a change of the metal and/or the organic linker. In this review, we briefly summarized gas separations and biomedical application.
Nanomaterials based on the transition-metal complexes are made from bottom-up assembly of metal ionsand organic ligands. These materials offer high degrees of structural designability and tunability derived from substitutions structural components. Here we describe the successful fabrications and physical properties of porous metal-organic nanotube and three-dimensional crystalline-oriented porous metal-organic framework nanofilm.
Two types of metal complex nanostructures constructed based on ‘interfacial coordination programming’ are described. One type involves metal complex oligomer wires prepared using stepwise complexation of metal ions with bis- and tris-tpy (tpy = 2,2’:6’,2”-terpyridine) ligands on tpy-terminated SAM on gold and silicon electrodes. The other type is a π-conjugated nanosheet comprising planar nickel bis(dithiolene) complexes prepared using a coordination reaction of benzenehexathiol with nickel ion at liquid-liquid or gas-liquid interface.
We designed and prepared a molecularly imprinted Ru complex catalyst on a SiO2 surface, whose ligand was used as a template, for regio- and shape- selective epoxidation of the terminal C=C bond of limonene. The designed molecularly imprinted Ru complex on the SiO2 surface was prepared in a step-by-step manner and characterized by solid-state NMR, XPS, BET, and Ru K-edge EXAFS. It was found that the molecularly imprinted Ru catalyst with an imprinted cavity exhibited regio- and shape-selective performances for limonene epoxidation.
Crystalline materials often undergo stimulus-responsive structural transitions leading to new functions. In light of the fact that peptides have high design possibilities and structural flexibility, I envisioned that ionic crystals of cyclic metallo-peptides would demonstrate dynamic behaviors in the solid state within a flexible hydrogen-bonding network. Herein, I describe the structural mobilities of crystalline nano-cavities of peptide metallo-macrocycles. By the study of the water inclusion process established by single crystal X-ray analysis and thermal studies (TG·DSC), the stepwise structural changes accompanying the release of included water molecules were observed with keeping single crystallinity. Notably, in the case of NO3 salts, the release of all the included water molecules was found to regulate the opening and closing of the cavities through close cooperation between ligand exchange and internal hydrogen-bond switching.