Search

C47H37Fe2NO4P2Se2, monoclinic, P21/n (no. 14), a = 12.8144(11) Å, b = 17.9714(15) Å, c = 19.1077(17) Å, β = 104.329(4)°, V = 4263.5(6) Å3, Z = 4, R gt (F) = 0.0420, wR ref (F 2) = 0.0968, T = 298(2) K.

In this work, Eu-MOF has been synthesized and has excellent luminescence recognition ability for Fe3+ and TNP with good selectivity and high sensitivity via luminescence quenching.

Four organotin(iv) complexes have been designed and synthesized from the reactions of R2SnO (R = Me, Ph) with the corresponding ligands norfloxacin and levofloxacin. And the cytostatic and antifungal activity test have been done.

The incorporation of Sc3+ can stabilize calcite-phase LuBO3:Ce3+ to grow large-sized single crystals but leads to the significant degradation of scintillation performance.

The active sites of [FeFe]-hydrogenase promoted by Fe/E (E = S, Se) clusters have attracted considerable interest due to their significance in understanding the interconversion of hydrogen with protons and electrons. As an extension of the study on Fe/Se clusters related to H-cluster model compounds of [FeFe]-hydrogenase, a series of tertiary phosphine substituted Fe/Se carbonyls were successfully prepared. The treatment of Fe

Density functional theory (DFT) calculations on Fe(2)S(2)(CO)(6−2n)(PMe(3))(2n) for n = 0, 1, and 2 reveal that the most electron-rich derivatives (n = 2) exist as diferrous disulfides lacking an S–S bond. The thermal interconversion of the Fe(II)(2)(S)(2) and Fe(I)(2)(S(2)) valence isomers is symmetry-forbidden. Related electron-rich diiron complexes [Fe(2)S(2)(CN)(2)(CO)(4)](2−) of an uncertain structure are implicated in the biosynthesis of [FeFe]-hydrogenases. Several efforts to synthesize electron-rich derivatives of Fe(2)(μ-S(2))(CO)(6) (1) are described. First, salts of iron persulfido cyanides [Fe(2)(μ-S(2))(CO)(5)(CN)](−) and [Fe(2)(μ-S(2))(CN)(CO)(4)(PPh(3))](−) were prepared by the reactions of NaN(tms)(2) with 1 and Fe(2)(μ-S(2))(CO)(5)(PPh(3)), respectively. Alternative approaches to electron-rich diiron disulfides targeted Fe(2)(μ-S(2))(CO)(4)(diphosphine). Whereas the preparation of Fe(2)(μ-S(2))(CO)(4)(dppbz) was straightforward, that of Fe(2)(μ-S(2))(CO)(4)(dppv) required an indirect route involving the oxidation of Fe(2)(μ-SH)(2)(CO)(4)(dppv) (dppbz = C(6)H(4)-1,2-(PPh(2))(2), dppv = cis-C(2)H(2)(PPh(2))(2)). DFT calculations indicate that the oxidation of Fe(2)(μ-SH)(2)(CO)(4)(dppv) produces singlet diferrous disulfide Fe(2)(μ-S)(2)(CO)(4)(dppv), which is sufficiently long-lived as to be trapped by ethylene. The reaction of 1 and dppv mainly afforded Fe(2)(μ-SCH=CHPPh(2))(μ-SPPh(2))(CO)(5), implicating a S-centered reaction.

Phosphate bond cleavage is essential to physiological, antibacterial, or antitumor activity, as well as the elimination of chemical warfare agents. In this work, three transition metal binuclear complexes (Cu2LCl4, Co2LCl4, and Zn2LCl4) with a novel hexadentate imidazole derivative (L) were conveniently ‘one-pot’ synthesized to test their ability to cleave phosphate diesters, c-Myc oligonucleotides, and plasmid pBR322 DNA. Single crystal structures indicated that each central metal ion is penta-coordinated for each binuclear complex. Cu2LCl4 with a space group of P21/n is monoclinic, and Zn2LCl4 with a P space group is triclinic. Co2LCl4 with a C2/c space group is monoclinic and cis-configurational. Unfortunately, the tested complexes displayed low activity in the hydrolysis of two diesters and pBR322 plasmid DNA (although stronger ability was exhibited for c-Myc) used in this work, which is probably ascribed to the lack of bimetallic cooperation due to a relatively larger metal–metal distance in excess of 10 A. Density function theory (DFT) calculation provides evidence for the highest activity of Co2LCl4 among these three complexes in the hydrolysis reaction. With respect to the oxidative cleavage, only Cu2LCl4 displayed catalytic activity for these substrates in this work. As compared to the hydrolytic cleavage, the Cu2LCl4-mediated oxidative cleavage or destruction of each substrate was more efficient, and was accompanied by an excess of six orders of magnitude (approximately 7.75 million-fold) rate acceleration in the oxidative cleavage of HPNP, probably originating from the dominant nucleophilic attack of a greater amount of reactive hydroxyl free radicals against hydroxyl anions. The HPNP oxidative cleavage produces one attractive non-lactone phosphate monoester due to the direct attack of metal-activated hydroxyl radicals.

A novel visible-light photoredox catalysis protocol for the effective and efficient synthesis of 3-substituted chroman-4-ones and 2,3-dihydroquinolin-4(1H)-ones via tandem radical addition/cyclization of alkenyl aldehydes has been described. This reaction features a broad substrate scope, mild reaction conditions, and good functional group tolerance character.

In this article, six new Fe3S2 cluster complexes Fe3(µ3S)2(CO)7[(Ph2P)2NR] (1-6) (R = (CH2)2CH3, CH(CH3)2, (CH2)3CH3, CH2CH(CH3)2, p-C6H4CCH and m-C6H4CCH) were successfully synthesized by reactions of Fe3S2(CO)9 and the corresponding aminodiphosphines under refluxing toluene. Meanwhile, treatment of Fe3S2(CO)9 and (Ph2P)2NCH(CH3)Ph afforded two new Fe3S2 cluster complexes Fe3(µ3-S)2(CO)7[(Ph2P)2NCH(CH3)Ph] (7) and Fe3(µ3-S)2(CO)7[(κ2-Ph2P)2NCH(CH3)(Ph)] (8). Complexes 1–8 were characterized by elemental analysis, FT-IR, NMR spectroscopy, and especially X-ray crystallography. The elctrochemical properties were investigated by cyclic voltammetry, showing that they all have electrocatalytic ability for the reduction of protons to H2.

A series of Bi

The reactions of (μ-PhCH2Se)2Fe2(CO)6 (A) with the bisphosphine ligands [L = Ph2PCH2PPh2 (dppm), cis-Ph2PC2H2PPh2 (dppv), and (Ph2P)2N(n-Pr) (dppn)] under various experimental conditions have been studied. Reaction of A with dppm and Me3NO in MeCN at room temperature to give (μ-PhCH2Se)2Fe2(CO)5(k-dppm) (1), where only one phosphorus atom of dppm is coordinated in a monodentate fashion to Fe2Se2 unit. Reaction of A with dppv and Me3NO in toluene/MeCN at room temperature to give (μ-PhCH2Se)2Fe2(CO)4(k2-dppv) (2), where two phosphorus atoms of dppv are chelated to a single iron. While the (μ-PhCH2Se)2Fe2(CO)4(μ-dppm) (3) and (μ-PhCH2Se)2Fe2(CO)4(μ-dppn) (4) can be prepared by treatment of A with 1 equiv of dppm or dppn in refluxing xylene, where the phosphine acts as a bidentate ligand. Interestingly, the C Se bond homolysis is detected in the reaction of A with dppn, and unexpected dppn-bridged complex (μ-Se)2Fe2(CO)4(μ-dppn) (5) is isolated. All the complexes were characterized by elemental analysis, FT-IR, NMR spectroscopy, as well as by X-ray diffraction analyses.

The chemistry of Fe2(μ-SH)2(CO)4(PPh3)2 (2HH) is described with attention to S-S coupling reactions. Produced by the reduction of Fe2(μ-S2)(CO)4(PPh3)2 (2), 2HH is an analogue of Fe2(μ-SH)2(CO)6 (1HH), which exhibits well-behaved S-centered redox. Both 2HH and the related 2MeH exist as isomers that differ with respect to the stereochemistry of the μ-SR ligands (R = H, Me). Compounds 2HH, 2MeH, and 2 protonate to give rare examples of Fe-SH and Fe-S2 hydrides. Salts of [H2]+, [H2HH]+, and [H2MeH]+ were characterized crystallographically. Complex 2HH reduces O2, H2O2, (PhCO2)2, and Ph2N2, giving 2. Related reactions involving 1HH gave uncharacterizable polymers. The differing behaviors of 2HH and 1HH reflect stabilization of the ferrous intermediates by the PPh3 ligands. When independently generated by the reaction of 2HH with 2,2,6,6-tetramethyl-1-piperidinyloxy, 2* quantitatively converts to 2 or, in the presence of C2H4, is trapped as the ethanedithiolate Fe2(μ-S2C2H4)(CO)4(PPh3)2. Evidence is presented that the Hieber-Gruber synthesis of 1 involves polysulfido intermediates [Fe2(μ-S n)2(CO)6]2- ( n > 1). Two relevant experiments are as follows: (i) protonation of [Fe4(μ-S)2(μ-S2)CO)12]2- gives 1 and 1HH, and (ii) oxidation of 1HH by sulfur gives 1.

Four novel isostructural lanthanide coordination complexes [Ln2(L)6(DMF)]n (Ln = Nd (1), Tb (2), Dy (3), Ho (4)) were successfully assembled under hydrothermal conditions with Ln3+ salts and 3,4,5-trifluorobenzeneseleninic acid (HL). All the complexes have been characterized by infrared spectroscopy (IR), elemental analysis, powder X-ray diffraction and single-crystal X-ray diffraction analyses. The structure analyses indicate that complexes 1–4 exhibit an infinite one-dimensional (1D) zig-zag chain structure. The solid-state photoluminescence property of complex 2 has been investigated at room temperature and it exhibits the characteristic emission bands derived from Tb3+ cation. In addition, the magnetic investigations of complexes 3–4 reveal weak antiferromagnetic interactions between LnⅢ (DyⅢ for 3, HoⅢ for 4) ions. Complexes 1–4 are rare examples of lanthanide(III) derivatives based on areneseleninic acids.

Six new triorganotin complexes, [(R3Sn)2(O2CC5H3NS)2]n (R = Me: 1; n-Bu: 2), [(R3Sn)2(O2CC6H4S)2]n (R = Me: 3; n-Bu: 4), [(R3Sn)2(O2CCH2S)2]n (R = Me: 5; n-Bu: 6) have been obtained by the reaction of R3SnCl (R = Me, n-Bu) with the corresponding dicarboxylate ligands (H2L1 = 6,6’-dithiodinicotinic acid, H2L2 = 2,2’-dithiodibenzoic acid, H2L3 = dithiodiglycolic acid). All the compounds were characterized by elemental analysis, IR, NMR, and X-ray crystallography. The structural analysis reveals that complexes 1–6 display various 2D metal-organic framework structures including wave-like, corrugated and double-layer, which is attributed to the twisting of the ligands around flexible S S bonds. Additionally, in vitro cytotoxic investigation of complexes 1–6 were also conducted by employing human cervix cell lines (HeLa) and human lung cancer cells (A549).

Four novel homochiral organotin phosphonates, namely, (R)-, (S)-[(Me3Sn)2(pemp)(H2O)]n (1, 2) and (R) -, (S)-[(Ph3Sn)2(pemp)2]n (3, 4) [pempH2 = (R)- or (S)-(1-phenylethylamino) methylphosphonic acid], were synthesized and characterized by X-ray diffraction analysis, elemental analysis, FT-IR, NMR (1H, 13C, 31P and 119Sn), TGA (thermogravimetric analysis) and CD (circular dichroism spectra). The structure analysis indicates that complex 1 displays 1D left-handed helical chain and complex 2 shows right-handed helical chain. These 1D chains are further linked into a 2D supramolecular network architecture through the intermolecular O–H⋯O interactions. Complexes 3 and 4 are isostructural that showing 1D infinite zig-zag chain structure. In addition, the molecules of complexes 3 and 4 are further linked through intermolecular C–H···π interactions into a 2D supramolecular structure. Furthermore, we preliminarily estimated in vitro cytostatic activity of complexes 1–4 against the human cervix tumor cells (HeLa) and the human hepatocellular carcinoma cells (HepG-2).

A new series of 4-carboxybenzenesulfonamide organotin(IV) complexes, [Me3Sn(O2CC6H4-SO2NH2-4)] (1), [n-Bu3Sn(O2CC6H4-SO2NH2-4)] (2), [Ph3Sn(O2CC6H4-SO2NH2-4)] (3), [(Me2Sn)4(μ3-O)2(μ2-OCH3)2(O2CC6H4-SO2NH2-4)2] (4), [(n-Bu2Sn)4(μ3-O)2(μ2-OCH3)2(O2CC6H4-SO2NH2-4)2] (5), [(n-Oct2Sn)4(μ3-O)2(μ2-OCH3)2(O2CC6H4-SO2NH2-4)2] (6), have been designed and synthesized from the reactions of 4-carboxybenzenesulfonamide with the corresponding triorganotin(IV) chloride or diorganotin(IV) oxide. The six complexes were characterized by elemental analysis, FT-IR, NMR (1H, 13C and 119Sn) spectroscopy, as well as by single crystal X-ray diffraction analysis. X-ray diffraction discloses that complexes 1–3 represent mononuclear tin(IV) monomer, and complexes 4–6 adopt tetranuclear tin(IV) ladder-like structure containing two deprotonated ligands linked by three alternate Sn2O2 four-membered rings. Analysis of the non-covalent intermolecular contacts in all complexes reveals the existence of the N H⋯O C, N H⋯O S and Sn⋯O interactions, which play significant function in the supramolecular construction. Furthermore, complexes 1–5 were evaluated for their in vitro cytostatic activity against human cervical carcinoma cell lines (HeLa) and human hepatocellular carcinoma cell lines (HepG-2). The pilot study has confirmed that some of these novel organotin(IV) complexes exhibited high in vitro cytostatic activity.

A new series of fluorobenzenetelluronic triorganotin(IV) esters, namely (R3Sn)4H2L (H6L1 = [3-FC6H4TeO(OH)3]2, R = Me: 1, R = Ph: 2; H6L2 = [3,4-F2C6H3TeO(OH)3]2, R = Me: 3, R = Ph: 4; H6L3 = [3,4,5-F3C6H2TeO(OH)3]2, R = Me: 5, R = Ph: 6), have been synthesized by the reaction of deprotonated fluorobenzenetelluronic acid ligands with the corresponding R3SnCl (R = Me, Ph). All the complexes have been characterized by means of elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectroscopy and X-ray crystallography. Structural analyses of the complexes reveal that they are isostructural and display an almost planar four-membered Te2(μ2-O)2 core in the center. Each Te atom adopts a distorted octahedral geometry and each Sn atom adopts a distorted tetrahedral geometry. Complexes 1, 3, 5, and 6 form one-dimensional supramolecular structures, while 2 and 4 form two-dimensional supramolecular structures by intermolecular C–H⋯F or C–H⋯O interactions. Preliminary in vitro cytostatic studies show that these fluorobenzenetelluronic triorganotin esters exhibit effective cytostatic activity against a human cervical adenocarcinoma cell line (HeLa) and a human hepatocellular carcinoma cell line (HepG-2). For further discerning the apoptotic properties of cytostatic activity, the level of apoptosis was determined by flow cytometry (FACS assay). The DNA-binding properties of these complexes with calf thymus DNA (CT-DNA) and protein-binding properties with BSA were investigated by means of fluorescence titration. The results indicate that all the complexes could quench the intrinsic fluorescence of BSA in a static way.

A Lewis acid-catalyzed one-pot aza-Michael addition/fragmentation/sulfinyl conjugate addition/cyclization cascade of o-QMs and arylsulfonyl hydrazides is described for the first time. This technology engages a broad range of substrates with both components under mild conditions, giving the corresponding valuable 3-sulfonylbenzofurans in generally good yields. These investigations show the use of arylsulfonyl hydrazides as nucleophiles for the first time in catalytic C–N and C–S bond formation with o-QMs.

Inspired by the metal active sites of [FeFe]- and [NiFe]‑hydrogenases, a series of mononuclear Ni(II) ethanedithiolate complexes [{(Ph2PCH2)2×}Ni(SCH2CH2S)] (X = NCH2C5H4N-p (2a), NCH2C6H5 (2b), NCH2CHMe2 (2c), and CH2 (2d)) with chelating diphosphines were readily synthesized through the room-temperature treatments of mononuclear Ni(II) dichlorides [{(Ph2PCH2)2×}NiCl2] (1a-1d) with ethanedithiol (HSCH2CH2SH) in the presence of triethylamine (Et3N) as acid-binding agent. All the as-prepared complexes 1a-1d and 2a-2d are fully characterized through elemental analysis, nuclear magnetic resonance (NMR) spectrum, and by X-ray crystallography for 1b, 2a-2d. To further explore proton-trapping behaviors of this type of mononuclear Ni(II) complexes for catalytic hydrogen (H2) evolution, the protonation and electrochemical proton reduction of 2a-2c with aminodiphosphines (labeled PCNCP = (Ph2PCH2)2NR) and reference analogue 2d with nitrogen-free diphosphine (dppp = (Ph2PCH2)2CH2) are studied and compared under trifluoroacetic acid (TFA) as a proton source. Interestingly, the treatments of 2a-2d with excess TFA resulted in the unexpected formation of dinuclear Ni(II)-Ni(II) dication complexes [{(Ph2PCH2)2×}2Ni2(μ-SCH2CH2S)](CF3CO2)2 (3a-3d) and mononuclear Ni(II) N-protonated complexes [{(Ph2PCH2)2N(H)R}Ni(SCH2CH2S)](CF3CO2) (4a-4c), which has been well supported by high-resolution electrospray ionization mass spectroscopy (HRESI-MS), NMR (31P, 1H) as well as fourier transform infrared spectroscopy (FT-IR) techniques, and especially by X-ray crystallography for 3d. Additionally, the electrochemical properties of 2a-2d are investigated in the absence and presence of strong acid (TFA) by using cyclic voltammetry (CV), showing that the complete protonation of 2a-2d gave rise to dinuclear Ni2S2 species 3a-3d for electrocatalytic proton reduction to H2.

The development of associated alpha particle scintillation screen that takes into account high spatial resolution, ultrafast temporal resolution, and high signal-to-noise ratio is the key to promote the “fingerprint” technology in the field of explosive detection—the deuterium–tritium (D–T) reaction associated particle neutron generator (APNG). Herein, the highly uniform and densely packed ZnO:Ga nanorod arrays, as designed alpha particle scintillation screen for the APNG, is proposed and prepared on a ZnO-seeded substrate by a radio frequency magnetron sputtering and hydrothermal method. The simulation results show that the theoretical cutoff thickness is 7.6 μm for 3.5 MeV alpha particles, and the increase in array spacing is conducive to suppress transverse light output and improve its light output efficiency and spatial resolution simultaneously. Through hydrogen annealing treatment, the slow decay component is completely suppressed and the integrated intensity of the fast decay component with a rising edge response of 1 ns is significantly enhanced by nine times.

The application of LuBO