A porous Cu(I)-MOF was constructed from CuI and 1-benzimidazolyl-3,5-bis(4-pyridyl)benzene. This Cu(I)-MOF can be a highly sensitive naked-eye colorimetric sensor to successively detect water and formaldehyde species in a single-crystal-to-single-crystal fashion. Solid-state guest-responsive luminescence is also used to monitor the sensing process.

A bifunctional robust and highly porous imidazolium-based ionic liquid decorated UiO-67 type MOF (UiO-67-IL, 1) was successfully constructed via solvothermal assembly of the imidazolium-based ligand and Zr(IV) ions. It exhibits a highly selective adsorption for CO over CH and N. Furthermore, 1 herein can be used as a highly active heterogeneous catalyst for CO cycloaddition with epoxides under atmospheric pressure with or without cocatalyst TBAB (n-BuNBr).

A new family of porous lanthanide-based coordination polymers with tunable luminescent properties based on reversible ion-dependent exchange was reported.

Using a temperature-dependent synthetic approach, four distinct new silver(I) coordination polymers resulting from the different conformations adopted by the flexible ligand at different temperatures were obtained.

The first example of highly efficient iodine enrichment based on a Cd(II)-triazole MOF (1) via both molecular sorption and ion-exchange approaches is reported.

A series of reactive group functionalized aromatics, namely 2-furaldehyde, 3-furaldehyde, 2-thenaldehyde, 3-thenaldehyde, o-toluidine, m-toluidine, p-toluidine, and aniline, can be absorbed by a CdL(2) (1; L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)-1,2,4-triazole) porous framework in both vapor and liquid phases to generate new G(n) [symbol: see text] CdL(2) (n = 1, 2) host-guest complexes. In addition, the CdL(2) framework can be a shield to protect the active functional group (-CHO and -NH(2)) substituted guests from reaction with the outside medium containing their reaction partners. That is, aldehyde-substituted guests within the CdL(2) host become "stable" in the aniline phase and vice versa. Moreover, 1 displays a very strict selectivity for these reactive group substituted aromatic isomers and can completely separate these guest isomers under mild conditions (i.e., 2-furaldehyde vs 3-furaldehyde, 2-thenaldehyde vs 3-thenaldehyde, and o-toluidine vs m-toluidine vs p-toluidine). All adsorptions and separations are directly performed on the single crystals of 1. More interestingly, these reactive group substituted aromatics readily transform to the corresponding radicals within the CdL(2) host upon ambient light or UV light (355 nm) irradiation. Furthermore, the generated organic radicals are alive for 1 month within the interior cavity in air under ambient conditions. Simple organic radicals are highly reactive short-lived species, and they cannot be generally isolated and conserved under ambient conditions. Thus, the CdL(2) host herein could be considered as a radical generator and storage vessel.

Coordination-driven self-assembly of discrete nanosized molecular cages has become one of the most active areas of supramolecular chemistry. 1 Over the past decade, extensive studies have been made on discrete molecular assemblies M x L y with various values of x and y. 2 Among these metal-ligand clusters, the assembly of M 2 L 4 tetragonal cage remains quite rare, although a few such d-block metal supramolecular complexes have appeared in the literature recently. 3 Canonical symmetric Ln 2 L 4 lanthanide cages have, to the best of our knowledge, never been described. This is clearly due to inherent difficulties in harmonizing the subtle relationship between the versatile coordination modes of the lanthanide metals (coordination numbers usually g8) and the ligand conformations in the synthetic cage systems. Lanthanide discrete cage-like assemblies, however, are of considerable interest in broad scientific areas, especially as the luminescent materials.We have recently reported a series of coordination polymers and supramolecular complexes based on bent five-membered heteroatom-ring-bridged ligands. 4 By taking into account the bent geometry of such spacers, we wondered if the five-membered heteroatom ring-bridged 3,3′-biphenylcarboxylate type ligands could be used as an "organic clip" 5 to bind lanthanide ions into discrete molecular cages, especially the Ln 2 L 4 tetragonal cages.Depending on this ligand-directed approach, 3 a series of lanthanide nanosized tetragonal cages Ln 2 L1 4 (Ln(III) ) La (1), Ce (2), Sm (3), Eu (4), and Tb (5) 6 The X-ray crystal structure analysis (Supporting Information) revealed that 1-5 are isostructural. They crystallize in the high-symmetry tetragonal space group, I4/m. For example 3, each Sm(2) node lies in a distorted singlecapped square antiprism coordination sphere (Figure 1), which is defined by eight carboxylic oxygen and one aquo oxygen donors and with Sm-O distances range from 2.457 to 2.576 Å. 7 For 1-5, the ligand donor to Ln(III) bond lengths simply reflect the ionic radius variation. 7 The most important structural feature of 1-5 is their cationic cage-like structure. As shown in Figure 1, four equivalent L1 ligands act as the desired organic clip to bridge two Ln(2) ions to form a tetragonal prismatic cage. It is interesting that the two phenyl rings on the same L1 ligand are basically coplanar, while the central triazole ring rotates by about 40°with respect to the phenyl plane and orients to the tangential direction of the cage. Such organized manner leaves an opening of ∼6.8 Å in the side of the cage. One (Figure 1). Top view of 3 shows that the four ligands crosswise arrange around the Ln(2)‚‚‚Ln(1)‚‚‚Ln(2) axis and the two Ln 2 L1 2 planes are perpendicular to each other, which results in the tetragonal cage canonical. There is a crystallographically imposed C 4 axis passing through these three Ln(III) ions and σ h mirror across the center of the molecule, leading to S 4 symmetry of the cage. The Ln‚‚‚Ln distance is ca. 11 Å, and the distance between the two ...

A novel acidic fluorescent probe 1 has been designed, synthesized, characterized and evaluated in vivo as optical imaging of intracellular H(+). The design strategy for the probe is based on the change in structure between spirocyclic (non-fluorescent) and ring-open (fluorescent) forms of rhodamine dyes. The probe exhibits high sensitivity, good photostability, excellent cell membrane permeability and strong pH dependence. The pH titration indicates that the fluorescence intensity increases more than 100-fold within the pH range of 4.2-6.0 with the pK(a) value of 4.85, which is valuable for studying acidic organelles in living cells. The fluorescent imaging of HepG2 cells also demonstrates that the designed probe has great value in monitoring intracellular H(+) within living cells.