Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.

http://science.sciencemag.org/content/sci/283/5405/1148.full.pdf

A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n

A geometrical analysis has been performed on π–π stacking in metal complexes with aromatic nitrogen-containing ligands based on a Cambridge Structural Database search and on X-ray data of examples in the recent literature. It is evident that a face-to-face π–π alignment where most of the ring-plane area overlaps is a rare phenomenon. The usual π interaction is an offset or slipped stacking, i.e. the rings are parallel displaced. The ring normal and the vector between the ring centroids form an angle of about 20° up to centroid–centroid distances of 3.8 A. Such a parallel-displaced structure also has a contribution from π–σ attraction, the more so with increasing offset. Only a limited number of structures with a near to perfect facial alignment exists. The term π–π stacking is occasionally used even when there is no substantial overlap of the π-ring planes. There is a number of metal–ligand complexes where only the edges of the rings interact in what would be better described a C–H⋯π attraction.

A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands

Self-Assembly of Discrete Cyclic Nanostructures Mediated by Transition Metals

3.7. Palladium Nanoparticles as Catalysts 888 3.8. Other Transition-Metal Complexes 888 3.9. Transition-Metal-Free Reactions 889 4. Applications 889 4.1. Alkynylation of Arenes 889 4.2. Alkynylation of Heterocycles 891 4.3. Synthesis of Enynes and Enediynes 894 4.4. Synthesis of Ynones 896 4.5. Synthesis of Carbocyclic Systems 897 4.6. Synthesis of Heterocyclic Systems 898 4.7. Synthesis of Natural Products 903 4.8. Synthesis of Electronic and Electrooptical Molecules 906

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20874-922.pdf

The Sonogashira Reaction: A Booming Methodology in Synthetic Organic Chemistry†

/pdf/metal-organic-frameworks-and-self-assembled-supramolecular-2xs948xxr9.pdf

Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

Molecular paneling via coordination

Figure Crystal structure of sphere 2b. Counterions and solvent are omitted for clarity. NW2/ 2003G186 Finite, Spherical Coordination Networks that Self-Organize from 36 Small Components Masahide Tominaga, Keisuke Suzuki, Masaki Kawano, Takahiro Kusukawa, Tomoji Ozeki, Shigeru Sakamoto, Kentaro Yamaguchi, and Makoto Fujita* 1 Department of Applied Chemistry, The University of Tokyo, CREST, Japan Science and Technology Corporation (JST), Bunkyo-ku, Tokyo 113-8656, Japan 2 Department of Chemistry and Materials Science. Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan 3 Chemical Analysis Center, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522 (Japan)

Finite, Spherical Coordination Networks that Self‐Organize from 36 Small Components

Selective encapsulation and isolation of molecules are one of the most attractive features of cagelike molecules.[1] Intermolecular chemical reactions of two or more substrates encapsulated in a molecular cage can be remarkably accelerated and suitably controlled as a result of the dramatically increased concentration and the strictly regulated orientation of the substrates in the cavity.[2] Such systems provide artificial mimics of the sophisticated active site of enzymes.[3] Recently we reported that structurally well-defined coordination cages (1 and 2), which self-assemble from six metal ions and four tridentate ligands, selectively encapsulate large organic molecules at the fixed position of the nanosized cavity.[4, 5] Thus, they are expected to facilitate intermolecular [2 2] photochemical reactions and control the stereoand regiochemistry in stringent geometrical environment. The photodimerization has been studied extensively in some media such as micelles, zeolites, organic hosts (for example, cyclodextrins and cucurbiturils),[6] and crystals.[7] However, a high degree of stereoand regiochemical control is still desired. Here we report remarkably accelerated, highly stereoregulated [2 2] photodimerization of acenaphthylenes (3)[8] and naphthoquinones (4)[9] within the coordination cages (1 and 2) in an aqueous medium that give rise to only syn and head-to-tail isomers. Quantitative formation of a syn dimer of acenaphthylene (3a) within cage 1 was clearly observed in the following experiment: An excess amount of 3a was suspended in a solution of 1 in D2O (2.0 m ) for 10 min at 80 C. Analysis of the D2O solution after filtration of free 3a by 1H NMR spectroscopy showed formation of the encapsulation complex 1 ¥ (3a)2 had occurred (Figure 1a). The signals of 3a were highly upfield-shifted as a result of the efficient encapsulation in the cavity. After the clear solution was irradiated (400 W) for 0.5 h at room temperature, the signals derived from 3a completely disappeared and one set of new signals appeared at 5.84, 5.61, 3.39, and 2.87 (Figure 1b). The signals of 1

Cavity-directed, highly stereoselective [2+2] photodimerization of olefins within self-assembled coordination cages.

An adamantanoid (H2O)10 cluster is formed within the hydrophobic cavity of a self-assembled coordination cage. This cluster is termed “molecular ice” because it is the smallest unit of naturally occurring Ic-type ice. X-ray structural analysis, coupled with neutron diffraction study, reveals that the molecular ice is formed not by a simple space-filling effect but by efficient molecular recognition within the cage via H2O:···π interaction.

Takahiro Kusukawa

Papers

Molecular paneling via coordination

Finite, Spherical Coordination Networks that Self‐Organize from 36 Small Components

Cavity-directed, highly stereoselective [2+2] photodimerization of olefins within self-assembled coordination cages.

Endohedral Clusterization of Ten Water Molecules into a “Molecular Ice” within the Hydrophobic Pocket of a Self-Assembled Cage

Ship-in-a-Bottle Synthesis of Otherwise Labile Cyclic Trimers of Siloxanes in a Self-Assembled Coordination Cage