[M8L4]8+-Type Squares Self-Assembled by Dipalladium Corners and Bridging Aromatic Dipyrazole Ligands for Iodine Capture.

Square-like metallamacrocyclic palladium(II) complexes [M8L4]8+ (1-7) were synthesized by reacting aromatic dipyrazole ligands (H2L1-H2L3 with pyromellitic arylimide-, 1,4,5,8-naphthalenetetracarboxylic arylimide-, and anthracene-based aromatic groups, respectively) with dipalladium corners ([(bpy)2Pd2(NO3)2](NO3)2, [(dmbpy)2Pd2(NO3)2](NO3)2, or [(phen)2Pd2(NO3)2](NO3)2, where bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine, and phen = 1,10-phenanthroline) in aqueous solutions via metal-directed self-assembly. Metallamacrocycles 1-7 were fully characterized by 1H and 13C nuclear magnetic resonance spectroscopy and electrospray ionization mass spectrometry, and the square structure of 7·8NO3- was further confirmed via single crystal X-ray diffraction. These square-like metallamacrocycles exhibit effective performance for iodine adsorption.

A highly sensitive C3-symmetric Schiff-base fluorescent probe for Cd2+.

A new C3-symmetric Schiff-base fluorescent probe (L) based on 8-hydroxy-2-methylquinoline has been developed. As expected, the probe L can display high fluorescent selectivity for Cd(2+) over Zn(2+) and most other common ions in neutral ethanol aqueous medium. Moreover, the mechanism of the L-Cd(2+) complex has been confirmed by X-ray crystallography and density functional theory calculation results. More importantly, L could be used to image Cd(2+) within living cells.

Programmable Self-Assembly of Heterometallic Palladium(II)-Copper(II) 1D Grid-Chain using Dinuclear Palladium(II) Corners with Pyrazole-Carboxylic Acid Ligands.

A novel heterometallic diPdII -diCuII grid-chain, {[(bpy)4 Pd4 Cu2 L4 ](NO3 )4 }n (2; bpy=2,2'-bipyridine), was synthesized through a programmable self-assembly approach from the molecular corners [(bpy)2 Pd2 (HL)(L)](NO3 ) (1) as linkers with CuII nitrate by using the bifunctional H2 L ligand featuring primary (pyrazole) and secondary (benzoic acid) groups. Structural analysis revealed that 1D structure 2 consists of one [Cu2 (O2 CPh)4 ]n unit as a bridge and two [(bpy)2 Pd2 L2 ]n corners. Additionally, the catalytic effect of the heterometallic synergy on the Suzuki coupling reaction by using 2 was further explored.

A new quinoline-based fluorescent probe for Cd(2+) and Hg(2+) with an opposite response in a 100% aqueous environment and live cell imaging.

A new quinoline-based fluorescent probe was synthesized and characterized. Probe showed opposite fluorescence responses toward Cd(2+) (turn-on) and Hg(2+) (turn-off) in a 100% aqueous environment. X-ray crystallography analysis and TD-DFT calculations showed the different mechanisms of CHEF-based for -Cd(2+) and PET-based for -Hg(2+) caused by different binding modes and different electronic transfer patterns. The detection limits for the analysis of Cd(2+) and Hg(2+) ions were found to be 3.9 × 10(-8) M and 9.8 × 10(-7) M, respectively. Its in vivo sensitivities to Cd(2+) and Hg(2+) were demonstrated in the EC9706 cell line with the use of a laser scanning fluorescence microscope.

A dual functional probe for "turn-on" fluorescence response of Pb(2+) and colorimetric detection of Cu(2+) based on a rhodamine derivative in aqueous media.

A dual functional probe L based on rhodamine was devised and synthesized. Probe L can sense Pb(2+) and Cu(2+) in aqueous solution through two approaches: a significant fluorescence enhancement caused by Pb(2+) and a visible color change from colorless to orchid induced by Cu(2+). Competitive experiments showed that probe L had high fluorescence sensitivity for Pb(2+) and excellent colorimetric selectivity for Cu(2+) over many environmentally relevant ions. The mechanisms of L for sensing Pb(2+) and Cu(2+) have been well demonstrated by ESI-MS, (1)H NMR titration, IR, the crystal structure of L-Pb(2+) and density functional theory calculation of L-Cu(2+). In addition, fluorescence image detection of Pb(2+) in living cells displayed an enhanced fluorescence effect.

Ionic liquid directed syntheses of water-stable Eu- and Tb-organic-frameworks for aqueous-phase detection of nitroaromatic explosives.

Reactions of lanthanide nitrate, 1,3,5-benzenetrisbenzoic acid (H3BTB) and [RMI]Br ionic liquids (RMI = 1-alkyl-3-methylimidazolium; R = ethyl, propyl, butyl, amyl, or hexyl), gave rise to two novel lanthanide metal-organic frameworks (Ln-MOFs) [Ln(BTB)H2O], where Ln = Eu , Tb . In addition to helping solubilise the starting materials under the reaction conditions there is evidence that [RMI]Br itself can play a structure directing role and is intimately involved in template ordering in [Ln(BTB)H2O], even though neither the [RMI](+) cation nor the Br(-) anion is occluded into the ultimate structure. and are isostructural and consist of infinite rod-shaped lanthanide-carboxylate building units which are further bridged by trigonal-planar BTB ligands to give noninterpenetrated open 3D frameworks featuring a (6,6)-connected topology with the point symbol (4(4)·6(7)·8(4))(4(8)·6(7)). Importantly, the strong emission of and dispersed in water prompted us to explore their application for detection of different nitroaromatics in an aquatic system. and show similar selectivity and sensitivity towards the presence of trace amounts of nitroaromatic analytes in the aqueous phase, showing potential as explosive sensors.

Self-assembly of an unprecedented polyoxomolybdate anion [Mo20O66]12- in a giant peanut-like 62-core silver-thiolate nanocluster.

A polyoxometalate-templated silver thiolate nanocluster, [Ag62(S(t)Bu)40(Mo20O66)(Mo6O19)3(CH3CN)2]·(CF3SO3)4 (1), has been isolated, in which a giant peanut-like silver(i)-thiolate cluster [Ag62(S(t)Bu)40](22+) encapsulates an unprecedented [Mo20O66](12-) polyoxoanion core. It opens a new approach for the synthesis of both elusive polyoxometalates and high-nuclearity silver(i)-thiolate nanoclusters.