Highly Selective Enamination of ß-ketoesters Catalyzed by Interlocked [Cu8 ] and [Cu18 ] Nanocages.

Interlocking cages are of great interest due to their fascinating structures and potential applications. However, the interlocking of different cages has not been previously reported. Herein, quadruply interlocked [Cu8 ] and [Cu18 ] nanocages have been constructed and structurally characterized in cationic metal-organic framework {[CuI Cu4 II (XN)4 (PTA)4 (H2 O)4 ]0.5 SO4 ⋅5 H2 O⋅EtOH}n (1). 1 can trap the anionic pollutant CrO4 2- and the radioactive-contaminant simulant ReO4 - with an uptake capacity of 83.2 and 218 mg g-1 , respectively. Catalytic investigations reveal 1 is an efficient heterogeneous catalyst for the enamination of ethyl acetoacetate with aniline and the turnover frequency (TOF) can reach a record value of 4000 h-1 . More importantly, 1 represents the first of a catalyst of enamination to exhibit excellent size selectivity on different substrates. The robust catalyst can be reused at least ten times without obvious loss in catalytic activity.

Water Stable [Tb4] Cluster-Based Metal-Organic Framework as Sensitive and Recyclable Luminescence Sensor of Quercetin.

A novel 3D metal-organic framework (MOF){[Tb3(CBA)2(HCOO)(µ3-OH)4(H2O)]·2H2O·0.5DMF} n (S-1) was synthesized by the solvothermal method. The crystal structure indicates that [Tb4O4] cubane clusters self-assemble into an infinite chain by sharing vertex, which is further linked to adjacent chains through 1,1-cyclobutanedicarboxylic acid ligand (H2CBA), resulting in a honeycomb arrayed framework. S-1 possesses excellent water stability and still retains intact structure after exposure to water for 10 weeks or boiling water for 10 weeks. Interestingly, S-1 acts as a luminescence sensor to selectively and sensitively detect quercetin with the limit of detection (LOD) as low as 0.23 ppm (7.6 × 10-7 M). The relationship between relative luminescence intensity and concentration obeys linear in the range of 0-300 ppm (0-993 µM), which allows quantitative detection of quercetin. Importantly, S-1 can be reused at least six times with almost no change in luminescent intensity. Compared with the high performance liquid chromatography-mass spectrometry (HPLC-MS) method, S-1 was used to determine the content of quercetin in onionskin and apple peel samples with satisfactory results. Furthermore, a portable S-1 test paper is also developed and expected to be applied in practice. To our knowledge, S-1 is the first example of MOFs as luminescent sensor for quercetin.

Unique (3,4,10)-Connected Lanthanide-Organic Framework as a Recyclable Chemical Sensor for Detecting Al(3.).

Three isostructural Ln-BTB frameworks (Ln = Eu (1), Dy (2), Yb (3)) were synthesized and structurally characterized, in which mononuclear and trinuclear [Ln3] units as nodes construct unprecedented (3,4,10)-connected 3D frameworks with (4·6·8)4(4·8(2))2(4·8(5))(6(2)·8(4))(4(5)·6(8)·8(26)·10(6)) point symbol. The luminescent investigations revealed that compound 1 can sensitively and selectively detect Al(3+), but comparably compound 2 could not detect Al(3+) among various cations. More importantly, 1 as an Al(3+) sensor can be reused at least five times, which represents the first recyclable metal organic framework (MOF)-supported Al(3+) sensor. Additionally, magnetic investigations on 2 also were carried out, showing a single-molecule-magnet behavior.

Structures and magnetic properties of several phenoxo-O bridged dinuclear lanthanide complexes: Dy derivatives displaying substituent dependent magnetic relaxation behavior.

Nine dinuclear Ln(iii) complexes, [Ln(dbm)2(L)]2 (Ln = Eu (), Tb (), Dy (), Ho (), Er ()) and [Ln(dbm)2(L')]2 (Ln = Tb (), Dy (), Ho (), Er ()) (dbm = 1,3-diphenyl-1,3-propanedione, HL = 2-[[(4-methoxy-phenyl)imino]methyl]-8-hydroxy-quinoline and HL' = 2-[[(4-ethoxyphenyl)imino]methyl]-8-hydroxyquinoline) have been synthesized, and structurally and magnetically characterized. The nine complexes are all phenoxo-O bridged binuclear complexes, in which Ln1 and Ln1a are in an eight-coordinated environment bridged by two phenoxido oxygen atoms of two 8-hydroxyquinoline Schiff base ligands. Although complexes and have very similar structures, magnetic studies reveal that they exhibit different magnetic relaxation behaviors with the effective barriers (ΔE/kB) of 34.5 K for and 67.6 K for . The dissimilar dynamic magnetic behaviors of and mostly result from the different electron-donating effect induced by the two alkoxy (-OCH3 and -OC2H5) of the 8-hydroxyquinoline Schiff base ligands. Meanwhile, for complexes , , and , there are no observed magnetic relaxation behaviors under a zero dc field. In addition, the luminescence properties of , and were studied.