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An unprecedented nanoscopic polyhedral cage-containing metal-metalloporphyrin framework, MMPF-1, has been constructed from a custom-designed porphyrin ligand, 5,15-bis(3,5-dicarboxyphenyl)porphine, that links Cu(2)(carboxylate)(4) moieties. A high density of 16 open copper sites confined within a nanoscopic polyhedral cage has been achieved, and the packing of the porphyrin cages via an "ABAB" pattern affords MMPF-1 ultramicropores which render it selective toward adsorption of H(2) and O(2) over N(2), and CO(2) over CH(4).

A mesoporous metal-organic framework possessing permanent porosity has been synthesized and characterized for the first time.

Highly stable Cu(I)-olefin coordination oligomers and polymers have been successfully prepared and applied to construct metal-organic frameworks (MOFs) with interesting physical and chemical functions in recent years. In this review, we present the olefin-Cu(I) coordination oligomers and polymers and their novel physical properties. From structure to functions, particular emphasis is placed on the coordination and organometallic chemistry of olefin-Cu(I) coordination oligomers and polymers, their structures and potential applications as solids possessing unusual physical functional properties such as electrochemical, chiral separation, fluorescent sensing and ferroelectricity.

Abstract: The crystal structures of amarine (1) and isoamarine (2), important intermediates in the preparation of 1,2-diphenyl-diaminoethane, were successfully determined. Their allylation products, 1,3-diallyl amarine (1)(CH2 ph name="dbnd" />CH2)2Br (3) and isoamarine bromide (2)(CH2 ph name="dbnd" />CH2)2Br (4) [the crystal structures of (1)(CH2 ph name="dbnd" />CH2)2PF6(3-Br+PF6) and (2)(CH2 ph name="dbnd" />CH2)2PF6 (4-Br+PF6) are also successfully determined to confirm allylation products], react with CuBr to afford (1)2(CH2 ph name="dbnd" />CH2)4(Cu2Br4) (5) and (2)(CH2 ph name="dbnd" />CH2)2(Cu2Br3) (6), respectively. Crystal structures of 5 and 6 reveal that 5 is an anion discrete complex without olefin moiety coordination, and 6 has a 1D infinite chain with olefin moiety coordination as a bridging spacer. The fluorescent emission spectra of 5 (λ emax =570nm) and 6 (λ emax =642nm) were measured, and display a significant difference that can be used for solid state fluorescent sensing them. [Copyright &y& Elsevier]

Abstract: The solvothermal reactions of N-allyl imidazole with CuIX (X=Cl, Br) afford two unprecedented 3D copper(I)–olefin coordination polymer Cu2X2(N-allyl imidazole) (X=Cl for 1; Br for 2). This is the first 3D copper(I)–olefin coordination polymer synthesized in directed method, compared to most of olefin–Cu(I) coordination polymers prepared by electrochemical method. Of practical interest is that both of them contain 1D zigzag ladder chain composed of basic Cu2X2 dimer unit. Photoluminescent measurements show that 1 displays blue fluorescent emission while 2 has red fluorescent emission at room temperature. [Copyright &y& Elsevier]