Post-synthetic coordination modification has proven to be a general and powerful approach for the functionalization of porous coordination polymers or metal-organic frameworks (MOFs). Metal-azolate frameworks (MAFs) are an important subclass of MOFs. In this account, the progress in the coordination post-synthetic modifications of an exceptionally robust pillared-rod MAF, featuring mixed μ-chloride and μ₃-triazolate bridges as the rods and linear bistriazolates as the pillars, and its structural analogues with different transition metal ions and/or expanded organic bridging ligands are summarized and discussed. Through removal of the terminal coordinated solvent molecules, redox of the metal ions, and exchange of the anionic inorganic bridging ligands in the rods, significantly enhanced performances can be realized in carbon dioxide capture, photocatalytic carbon dioxide reduction, photocatalytic hydrogen generation, electrolytic water oxidation and oxidation of ethylbenzene.

Transition-metal-catalyzed C–C bond(s) formations are one of the most fundamental organic transformations, where the design of transition metal catalysts is the key of success. To activate two coupling partners simultaneously, we focused on the combination of a transition metal anion and a typical metal cation. The anionic transition metal center itself or own ligands are nucleophilically activated by the anionic charge, and the Lewis acidic typical metal cation activates the electrophilic counterpart. The synergy of these two metal centers located closely by electrostatic interaction enables cross-coupling and multicomponent coupling reactions. For instance, Co–Mg–Li system catalyzed cross-coupling reaction of alkyl halides with tertiary alkyl Grignard reagents to construct quaternary carbon center. The cross-coupling reaction of alkenyl ethers with aryl Grignard reagents via C–O bond cleavage could be achieved with Rh-Mg and Rh-Li combinations. The key catalytic active species containing Rh anion and Li cation was successfully isolated and characterized by X-ray crystallography to clarify a unique structure and reactivity of the Rh-Li complex. In addition, we successfully connected dimerizative transformation of 1,3-dienes promoted by a neutral Ni complex and a C–C bond formation with carbon electrophiles promoted by an anionic Ni complex in one catalytic cycle. The isolation of and structural insight into the anionic Ni complexes clarified the reaction mechanism and the origin of selectivity between multicomponent coupling reaction and competing cross-coupling reaction.

Supramolecular chemistry is the study of the entities based on the noncovalent interactions that play an essential role in controlling of biomolecular functions. In biological system, natural non-equilibrium system often depends on kinetically controlled pathway in addition to thermodynamically controlled mechanisms. In artificial supramolecular system, the recent advances have allowed numerous studies of molecular recognition behaviors and self-assembly processes. While they are generally thermodynamically controlled events, kinetic control of such processes is essential for the development of new supramolecular functional systems. Here we constructed kinetically controlled new supramolecular complexes based coordination chemistry. The guest uptake/release of host-guest system can be precisely controlled by the introduction of replaceable caps into the apertures of the macrocyclic metallohost. The kinetic study also unveiled the mechanism of host-gust binding where the metallohost uptakes the guest cation accompanied by the host reaction. By using a rigid bent ligand in which chelate coordination sites are introduced, we achieved the selective formation of kinetically-stable pentanuclear metallonanobelt by template-directed self-assembly.

In organometallic chemistry and homogeneous catalysis, the design and development of ancillary ligands are pivotal in order to control the central metalʼs reactivity. Whilst for classical late transition and precious metals, phosphines and N-heterocyclic carbenes have been successfully introduced to generate reactive, and even stereochemically defined sites, the search for suitable ancillary ligands for larger, more electropositive metals of s-, p-, d-, and f-block is often more difficult. We have introduced NNNN-type macrocyclic ligands based on cyclen (1,4,7,10-tetraazacyclododecane or [12]aneN₄, viz. the amido triamine ligand Me₃TACD and the neutral tetraamine ligand Me₄TACD. Both ligands have been used to solubilize insoluble solid-state hydrides, currently of interest as hydrogen storage materials, to give molecular hydrides with interesting reactivity toward small molecules such as H₂ and CO₂.