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Herein we report a discrete heterometallic Pd 4 Cu 8 L 8 cage with a tubular structure, which was synthesized by the assembly of copper metalloligands and Pd II ions in a stepwise manner. The Pd 4 Cu 8 L 8 cage has been unequivocally characterized by single-crystal X-ray diffraction, electrospray ionization-mass spectroscopy, and energy dispersive spectroscopy. The cage showed excellent catalytic activity in the epoxidation of styrene and its derivatives under conditions without using additional solvent, providing potential material for catalyzing the oxidation reactions.

The SiF 6 2- anions are in situ formed in the reactions of MF 2 (M = Cu 2+ , Zn 2+ , Ni 2+ , and Co 2+ ) salts and nitrogen-containing ligands in borosilicate glass tubes under solvothermal conditions and then used to further construct a family of metal-organic frameworks (MOFs). This in situ reaction demonstrates a new and facile strategy for the fabrication of MOFs based on SiF 6 2- .

Using water as the sole solvent, the bifunctional molecule tetrakis(methylthio)-1,4-benzenedicarboxylic acid (TMBD) was reacted with Cu(CH 3 CN) 4 BF 4 to form a robust microporous metal-organic framework (MOF, CityU-7) featuring Cu(I) ions being simultaneously bonded to the carboxyl and thioether donors. The MOF solid is stable in air and can be easily activated by heating, without the need for treatment with organic solvents. The subnanoscopic pores (ca. 0.6 nm) of the host net allow for uptake of CO 2 and H 2 O but exhibit lesser sorption for N 2 at 77 K. The microporous net can also be penetrated by I 2 molecules.

Three coordination polymers (CPs) with square-planar Cu II /Ni II N 4 subunits were formed in one step by subcomponent self-assembly, giving rise to an unprecedented linking variety of in situ embedded metalloligands and Cu I clusters. All CPs exhibit unusual visible-light adsorption. Enhanced photocatalytic activity and high selectivity were observed in the oxidation of benzene under visible-light irradiation.

A series of Ni-imidazolate cubic cages, one-dimensional and two-dimensional coordination polymers based on the cubic cages, have been prepared by solvothermal subcomponent self-assembly of 5-methyl-4-formylimidazole, m-xylylenediamine, and Ni(II) salts with varied anions. These compounds have been characterized by single-crystal X-ray diffractions, elemental analysis, IR spectra, and powder X-ray diffractions. The formation of an oligomerized coordination cage or an infinite coordination polymer depends on the anions chosen. An oligomerized 8-nuclear Ni-imidazolate cubic cage is formed when the anion Cl(-), Br(-), I(-), SCN(-), NO2(-), or NO3(-) is utilized in the reactions, and a two-dimensional coordination polymer based on the Ni-imidazolate cubic cage will be obtained when N3(-), (CN)2N(-), or (CN)3C(-) act as the anions. When only ClO4(-) or both ClO4(-) and [Ni(C4N2S2)2](2-) (C4N2S2 = dimercaptomaleonitrile) as anions exist in the reaction mixture, a ladder-like one-dimensional coordination polymer based on the Ni-imidazolate cubic cage and formate is formed unpredictably.

The reactions of 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tpt) with copper(I) halides under solvothermal or traditional conditions yielded two polymeric Cu(I) complexes [Cu2I2(tpt)]n (1) and [Cu3I3(tpt)]n (2), one mixed-valence Cu(I)-Cu(II) complex [Cu4Cl2I4(tpt)2] (3), and two Cu(II) complexes [CuBr(bpca)] (4) and [CuI(bpca)] (5) (bpca = bis(2-pyridylcarbonyl)amine). Complex 1 is a zigzag chain with tpt in a bis-bipyridine-like coordination mode, whereas complex 2 with tpt chelating three Cu(I) cations is a ladderlike coordination polymer. Complex 3 is mixed-valence, with Cu(I) in a distorted tetrahedral geometry and Cu(II) in a distorted square pyramidal geometry, forming a ladderlike supramolecular chain. Complexes 4 and 5 are the products of in situ hydrolysis of tpt involving the oxidation of Cu(I). The synthesis and characterization of complex 1, 2, and 5 indicated that Cu(I) cannot promote the hydrolysis of tpt. The theoretical study shows that the main effect for hydrolysis of tpt is the electron-withdrawing effect of metal ions.