Multiresponsive Luminescent Sensitivities of a 3D Cd-CP with Visual Turn-on and Ratiometric Sensing toward Al3+ and Cr3+ as Well as Turn-off Sensing toward Fe3.

By using the reduced Schiff base tricarboxylate ligand H3cip, one novel 3D Cd-based coordination polymer (Cd-CP) with the formula [Cd(Hcip)(bpea)0.5(H2O)]n (H3cip = 5-(3-carboxybenzylamino)isophthalic acid, bpea = 1,2-bis(4-pyridyl)ethane) has been solvothermally synthesized. The prepared Cd-CP possesses a 4-connected CdSO4 net based on dinuclear {Cd2} units. Luminescence measurements revealed that the complex exhibited ratiometric turn-on luminescence responses toward Al3+ and Cr3+ with a significant color change, which could be easily distinguished by the naked eye under ultraviolet light. Cd-CP can also respond to Fe3+ through a turn-off mechanism. Interestingly, the luminescence quenched by Fe3+@Cd-CP can be recovered and increased significantly by adding some competitive Al3+, while Cr3+ can only marginally increase the luminescence intensity of Fe3+@Cd-CP. Moreover, the detection of the three aforementioned metal ions can be realized by using Cd-CP-coated test papers, extending the potential application regions of the reported material to point-of-care tests and environmental field studies.

A novel (3,6)-connected CdII coordination polymer based on an ether-linked tricarboxylate ligand: synthesis, topology and luminescence sensing properties in aqueous solution.

A novel three-dimensional coordination polymer, namely, poly[[diaquabis(µ-4,4'-bipyridine)bis{µ3-5-[(2-carboxyphenoxy)methyl]isophthalato}tricadmium(III)] dimethylformamide monosolvate 2.5-hydrate], {[Cd3(C16H9O7)2(C10H8N2)2(H2O)2]·2C3H7NO·5H2O}n, was obtained by the reaction of ether-linked 5-[(2-carboxyphenoxy)methyl]isophthalic acid (H3L) with CdII salts in the presence of 4,4'-bipyridine (bpy) under solvothermal conditions. In this complex, the CdII centres are connected by the carboxylate ligands to form two-dimensional wave-like layers, which are pillared by bpy ligands and extended into a rare three-dimensional (3,6)-connected sqc27 framework. The complex demonstrated good water stability and strong luminescence emissions. It not only possesses excellent luminescence sensing activities toward Fe3+ and Cr2O72- in aqueous solution, but can also distinguish between Cr2O72- and CrO42- by luminescence. Furthermore, it could be simply and quickly regenerated at least five times. A study of the sensing mechanism indicated that luminescence quenching may be related to the energy competition between the complex and sensing analytes.

Tunable Light Emission and Multiresponsive Luminescent Sensitivities in Aqueous Solutions of Two Series of Lanthanide Metal-Organic Frameworks Based on Structurally Related Ligands.

Two series of lanthanide metal-organic frameworks (Ln-MOFs) from two structurally related flexible carboxylate-based ligands were solvothermally synthesized. H3L2 with additional -CH2- group provides more flexibility and different coordination modes and conformations compared with H3L1. As a result, 2-Ln MOFs are modulated from two-dimensional kgd of 1-Ln to three-dimensional rtl topological frameworks and further achieve enhanced chemical stability. The Eu- and Tb-MOFs exhibit strong fluorescent emission at the solid state because of the antenna effect of the ligands. Interestingly, the emissions can be tuned by simply doping Eu3+ and Tb3+ of different concentrations within the Eu xTb1- x MOFs. Notably, 2-Ln MOFs realize nearly white light emission by means of a trichromatic approach (red of Eu(III), green of Tb(III), and blue of the H3L2 ligand). Furthermore, 2-Ln MOFs also exhibit water stability and demonstrate high selective and sensitive sensing activities toward Fe(III) and Cr(VI) in aqueous solutions. The results further highlight the importance of the ligand flexibility on tuning MOF structures with improved structural stability and ion-sensing properties.

Cimicifoetones†A and B, Dimeric Prenylindole Alkaloids as Black Pigments of Cimicifuga foetida.

Two dimeric prenylindole alkaloids with a unique indole-benzoindolequinone skeleton, cimicifoetones A (1) and B (2), were isolated as black pigments from the rhizomes of Cimicifuga foetida. The structures were elucidated by spectroscopic methods including HRMS and 2D NMR, as well as single-crystal X-ray diffraction and computational chemical modeling techniques. Cimicifoetones A and B represented the first examples of dimeric indole alkaloids generated through [4+2] Diels-Alder cycloaddition between the prenyl side chain in one 3-prenylindole and the aromatic ring in another. The two compounds showed promising anti-proliferative activity on seven tumor cell lines with IC50 values in the range of 1.36-21.09 µm. Flow cytometric and western blot analysis revealed that compound 2 induced cell apoptosis via death receptor-mediated extrinsic and mitochondrial-mediated intrinsic pathways.