RESUMEN
Simple room-temperature self-assemblies between Cd2+ salts, SCN- and bisimidazole molecules at pH = 2 created three new organically templated thiocyanatocadmates [H2(L1)][Cd(SCN)4]·H2O (L1 = 1,4-bis(1H-imidazol-1-yl)benzene) 1, [H2(L2)][Cd(SCN)4] (L2 = 1,3-bis(2-methylimidazol-1-yl)propane) 2, and [H2(L3)][Cd2(SCN)6] (L3 = 1,4-bis(2-methyl-1H-imidazol-1-yl)butane) 3. X-ray single-crystal diffraction analysis reveals that (i) in 1-3, the SCN- groups doubly bridge the Cd2+ centers to form different thiocyanatocadmates: a linear chain in 1; a zigzag chain in 2; and a 2-D layer network (63 net) in 3; and (ii) in 1, via Nbase-HNSCN interactions, the L1 molecules extend the thiocyanatocadmate chains into a 2-D supramolecular layer, whereas in 2, the zigzag thiocyanatocadmate chains self-assemble into a 3-D supramolecular network via weak SS interactions. Photoluminescence analysis indicates that the three title compounds all emit light: blue light for 1 and 2 and green light for 3. At low temperatures, the emission positions of the three compounds hardly change, but the emission intensities are largely enhanced. Interestingly, after turning off the UV lamp, 1 and 2 still briefly emit light (ca. 2 s), which means that 1 and 2 possess phosphorescence properties. Phosphorescence lifetimes at 77 K are 1619 ms for 1 and 247 ms for 2.
RESUMEN
Under hydro(solvo)thermal conditions, four organic bidentate bridging N,N'-donor ligands 1,3-bis(2-methylimidazol-1-yl)propane (L1), 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl (L2), 1,2-bis(2-methyl-1H-imidazol-1-ylmethyl)benzene (L3) and 5,6,7,8-tetrahydroquinoxaline (L4) were employed to react with CuBr/CuI, generating four 2-D layered copper(i)-polymer coordination polymer materials [Cu2Br2(L1)] 1, [CuI(L2)] 2, [CuI(L3)] 3 and [CuI(L4)0.5] 4. In 1-4, different Cu-X motifs are found: a cubic Cu4Br4 core in 1; a castellated Cu-I single chain in 2; a rhombic Cu2I2 core in 3; and a staircase-like Cu-I double chain in 4. The 2-D layer networks of 1-3 can all be simplified into a simple 44 topology (planar for 1 and 3; wave-like for 2), while the 2-D layer network of 4 has a 63 topology. The photoluminescence behaviors of 1-4 under a UV lamp suggest that 1 and 2 possess fluorescence thermochromism properties. Under the UV lamp, with the decrease in temperature, (i) 1 exhibits a yellow-to-red emission; (ii) 2 exhibits a yellow-to-green emission; (iii) 3 always emits green light; and (iv) 4 never emits light. These are further confirmed by their emission spectra. From 297 K to 77 K, the emission of 1 exhibits a large red shift from 561 nm to 623 nm; the emission of 2 exhibits a large blue shift from 571 nm to 515 nm; only a minor red shift is observed for the emission of 3; and no peaks appear in the emission spectra of 4. The crystal data of 1 and 2 at different temperatures have been collected for revealing the origination of their fluorescence thermochromism properties. Based on the above investigations, the effect of the rigidity/flexibility of the organic ligand on the fluorescence thermochromism properties of copper(i)-polymer coordination polymer materials is discussed. The quantum yields at 297 K and the photoluminescence lifetimes at 297 K and 77 K for 1-3 were also measured for better understanding their photoluminescence properties.
RESUMEN
In this article, three bisimidazole derivatives (1,4-bis(2-ethylimidazol-1-yl)butane, L1; 4,4'-di(1H-imidazol-1-yl)-1,1'-biphenyl, L2'; and 1,3-bis(2-ethylimidazol-1-yl)propane, L3) were employed to solvothermally react with AgI in an acidic environment, creating three new 1-D chained iodoargentates [H(L1)][Ag5I6]·DMF (DMF = N,N'-dimethylformamide) 1, [L2][Ag3I5] (L22+ = 4,4'-di(1H-imidazol-1-ium)-1,1'-biphenyl) 2, and [H2(L3)][Ag2I4] 3. L22+ in 2 originated from the in situ N-alkylation of L2' with the CH3OH solvent. X-ray single-crystal diffraction analysis reveals that (i) in 1, Ag+ and I- aggregate to form a 1-D tube-like iodoargentate, which exhibits the same topology as the carbon tube; (ii) the chain structure of the iodoargentate in 2 is based on a kind of trinuclear Ag-I cluster, which can be viewed as a segment of the classical cubic M4I4 cluster; (iii) the chain structure of the iodoargentate in 3 is simple, which can be described as a linear arrangement of the AgI4 tetrahedra by sharing edges. The photoluminescence analysis reveals that at 77 K, (i) 1 and 2 emit strong yellow light with ms-grade photoluminescence lifetimes (5.460 ms for 1, 6.931 ms for 2); (ii) 3 possesses photochromic luminescence properties. Upon excitation at 254 nm, it emits blue-green light, whereas upon excitation at 365 nm, it emits yellow light.
RESUMEN
A novel method based on the molecularly imprinted solid-phase extraction (MISPE) procedure has been developed for the simultaneous determination of concentrations of sulfonylurea herbicides such as chlorsulfuron (CS), monosulfuron (MNS), and thifensulfuron methyl (TFM) in maize samples by liquid chromatography-tandem quadrupole mass spectrometry (LC-MS/MS). The molecularly imprinted polymer (MIP) for sulfonylurea herbicides was synthesized by precipitation polymerization using chlorsulfuron as the template molecule, 2-(diethylamino)ethyl methacrylate (DEAMA) as the functional monomer, and trimethylolpropane trimethacrylate (TRIM) as the cross-linker. The selectivities of the chlorsulfuron template and its analogs on the molecularly imprinted polymer were evaluated by high-performance liquid chromatography (HPLC). The extraction and purification procedures for the solid-phase extraction (SPE) cartridge with a molecularly imprinted polymer as the adsorbent for the selected sulfonylurea herbicides were then established. A molecularly imprinted solid-phase extraction method followed by high-performance liquid chromatography-tandem mass spectrometry for the determination of chlorsulfuron, monosulfuron, and thifensulfuron methyl was also established. The mean recoveries of these compounds in maize were in the range 75-110% and the limits of detection (LOD) of chlorsulfuron, monosulfuron, and thifensulfuron methyl were 0.02, 0.75, and 1.45 microg kg(-1), respectively. It was demonstrated that the MISPE-HPLC-MS/MS method could be applied to the determination of chlorsulfuron, monosulfuron, and thifensulfuron methyl in maize samples.