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Structural, optical and sensing properties of novel Eu(iii) complexes with furan- and pyridine-based ligands

A new family of imine and amine-based racemic ligands containing furan or pyridine as an aromatic donating ring [N,N?-bis(2-pyridylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine, L1; N,N?-bis(2-furanylmethylidene)-1,2-(R,R + S,S)-cyclohexanediamine, L2; N,N?-bis(2-pyridylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine, L3; and N,N?-bis(2-furanylmethyl)-1,2-(R,R + S,S)-cyclohexanediamine, L4] and their trifluoromethanesulphonate (CF3SO3-, OTf-) and nitrate Eu(iii) complexes is studied in acetonitrile (AN) solution. The stoichiometry and stabilities of the formed complexes are obtained by means of spectrophotometric titrations: when Eu(iii) triflate is used as a starting salt, two mononuclear species (1:1 and 1:2) are detected, while only the 1:1 complex is observed when the nitrate salt is employed. The stability of these complexes, as well as the geometry of their Eu(iii) environment, is significantly dependent on the nature of the ligand employed (imine or amine, furan or pyridine-based). DFT calculations show that all donor atoms are coordinated to the metal ion in the 1:1 EuL(L = L1-L4) species and suggest that the higher stability of the complexes with L1 and L2 with respect to L3 and L4 is mostly due to the higher degree of preorganization of the former species. The optical response of the imine-based L1 and L2 Eu complexes, produced by NO3- coordination, has been studied in order to assess their application as sensing devices. With both ligands, an increase of the emission intensity on the addition of the nitrate ion is observed. This is higher for the EuL2 complex and underlines the important role of the nature of the heteroaromatic ring. Finally, it is worth noting that an efficient energy transfer process from the ligand to the metal is present in the case of the 1:1 triflate Eu(iii) complex with the ligand L1. This journal is

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Stabilized Ru[(H2O)6]3+ in Confined Spaces (MOFs and Zeolites) Catalyzes the Imination of Primary Alcohols under Atmospheric Conditions with Wide Scope

Imines are ubiquitous intermediates in organic synthesis, and the metal-mediated imination of alcohols is one of the most direct and simple methods for their synthesis. However, reported protocols lack compatibility with many other functional groups since basic supports/media, pure oxygen atmospheres, and/or released hydrogen gas are required during reaction. Here we show that, in contrast to previous metal-catalyzed methods, hexa-aqueous Ru(III) catalyzes the imination of primary alcohols with very wide functional group tolerance, at slightly acid pH and under low oxygen atmospheres. The inorganic metal complex can be supported and stabilized, integrally, within either faujasite-type zeolites (Y and X) or a metal organic framework (MOF), to give a reusable heterogeneous catalyst which provides an industrially viable process well below the flammability limit of alcohols and amines.

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Temperature-induced self-assembly of two kinds Zn(II)-based coordination polymers with luminescence properties for application in sensing and adsorption

Temperature-induced self-assembly of coordination polymers (CPs) is of great importance for structural tunability and is quite necessary for further research on structure-property relationships. Two types of CPs {[Zn(L)(DMF)]¡¤3DMF}n (1) (H2L = 4,4?-(trans-cyclohexane-1,2 diyl)bis(azanediyl)bis(carbonyl)dibenzoic acid, DMF = N,N-dimethylformamide) and {ZnL}n (2) are synthesised by the reaction of Zn(NO3)2¡¤6H2O with H2L at different reaction temperatures. CP 1 with a one-dimensional structure is obtained at room temperature, 35 C and 45 C. CP 2 with a two-dimensional structure is prepared by heating at 75 C. When the temperature is further increased to 85 C, 95 C, 105 C and 120 C, CP 2 could still be obtained. Considering the decomposition of ligands and carbonization of solvents at high temperature, 120 C is chosen as the temperature endpoint in the experiment. Single crystal X-ray diffraction analysis indicates that 1 has a chain structure formed by binuclear metal clusters and a bridged carboxylate group. It also indicates that 2 shows a layered structure formed through intermolecular interactions between two adjacent chain motifs. The luminescence properties of 1 and 2 are explored at room temperature in the solid-state. The luminescence intensities of 1 and 2 are weak due to the N-H vibration of the ligand. In order to improve their luminescence properties, we attempt to introduce lanthanide(iii) ions into their channels. Only 2 can accept lanthanide ions Eu3+ and Tb3+ and still maintain its framework, as confirmed by PXRD. Besides, 2 can also sensitize them well. Therefore, the luminescence properties of 2 are improved vastly. The doped material can emit bright red and green light of Eu3+ and Tb3+. A series of EuxTb(1-x)@ZnL coordination polymers are prepared using a post-synthesis method to realize white light emission. The luminescent material Tb3+@ZnL shows a highly sensitive quenching effect to acetone among common solvents. The characteristic emission of Tb3+ could be quenched in the presence of 8 vol% acetone. In addition, 2 could selectively adsorb methylene blue (MB) due to its porosity and can act as a green adsorbent. Compared to 1, 2 is a promising multifunctional material for applications in photoluminescence, luminescent detection and dye adsorption.

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Synthesis of porous organic cage CC3 via solvent modulated evaporation

We demonstrate a Humidity Modulated Solvent Evaporation (HMSE) approach to promote the nucleation and growth of CC3 crystals. This approach relies on the gradual evaporation of dichloromethane (solvent) from a diluted concentration of CC3 precursors deposited on aluminum foil. The slow solvent evaporation allowed enough time for the organization and formation of CC3 porous organic cage. The solvent diffusion rate was modulated by the relative humidity in the system. The slow kinetics implied during the development of CC3 phase, allowed the formation of CC3 crystals. HRTEM, SAED, SEM, and XRD patterns were used as pivotal characterization techniques to follow and confirm the formation of CC3 crystals.

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Hydrolysis of the amide bond in N-acetylated l-methionylglycine catalyzed by various platinum(II) complexes under physiologically relevant conditions

The hydrolytic reactions between various Pt(II) complexes of the type [Pt(L)Cl2] and [Pt(L)(CBDCA-O,O?] (L is ethylenediamine, en; (¡À)-trans-1,2-diaminocyclohexane, dach; (¡À)-1,2-propylenediamine, 1,2-pn and CBDCA is the 1,1-cyclobutanedicarboxylic anion) and the N-acetylated l-methionylglycine dipeptide (MeCOMet-Gly) were studied by 1H NMR spectroscopy. All reactions were realized at 37 C with equimolar amounts of the Pt(II) complex and the dipeptide at pH 7.40 in 50 mM phosphate buffer in D2O. Under these experimental conditions, a very slow cleavage of the Met-Gly amide bond was observed and this hydrolytic reaction proceeds through the intermediate [Pt(L)(H2O)(MeCOMet-Gly-S)]+ complex. In general, it can be concluded that faster hydrolytic cleavage of the MeCOMet-Gly dipeptide was observed in the reaction with the chloride complex than with corresponding CBDCA Pt(II) complexes. The steric effects of the Pt(II) complex on the hydrolytic cleavage of the amide bond in the MeCOMet-Gly dipeptide were also investigated by 1H NMR spectroscopy. It was found that the rate of hydrolysis decreases as the steric bulk of the CBDCA and chlorido Pt(II) complexes increase (en > 1,2-pn > dach). These results contribute to a better understanding of the toxic side effects of Pt(II) antitumor drugs and should be taken into consideration when designing new potential Pt(II) antitumor drugs with preferably low toxic side effects.

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One-Pot Synthesis of New Organometallic Compounds with Platinum-Carbon Bond

Organometallic compounds of platinum containing ortho metalated para-nitro-benzamidate or 1-naphthalene-methylamine have been prepared by one-pot synthesis. The para-nitro-benzamidate [Pt{K2C,N-pNO2-C6H4C(O)NH}(R,R-DACH)] (compound 2) was obtained starting from [PtCl2(R,R-DACH)] and para-nitro-benzonitrile, which, in the reaction conditions, hydrolyzes to the corresponding amide and forms the dinuclear intermediate [Pt2{mu-N,O-pNO2-C6H4C(O)NH}2(R,R-DACH)2]SO4 (compound 1¡¤SO4) with HH or HT arrangement of the two bridging amidato ligands. Compound 1¡¤SO4, kept at 90 C for few hours, transforms into 2. The ortho-metalated PtII derivative with 1-naphthalene-methylamine [PtCl{K2C,N-C10H6CH2NH2}(DMSO)] (3) was obtained by direct reaction of [PtCl2(DMSO)2] with the amine. Unlike compound 2 that has no labile ligands, compound 3 has Cl and DMSO ligands that can be released, allowing the formation of cross-links with DNA. Oxidation of 3 to the PtIV counterpart was performed with PhICl2 (compound 4). Unexpectedly, although six-coordinate complexes of PtIV are considered to be inert, 4 underwent spontaneous isomerization from the mer to the fac isomer. All compounds have been fully characterized by multinuclear NMR spectroscopy, which has enabled complete assignment of all proton resonances. In the case of compound 2, a single-crystal X-ray investigation was also performed, showing, with the only exception of the puckered cyclohexane ring, a complete planarity of the complex frame, which could favor an intercalative interaction with DNA.

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Rare earth metal complexes based on beta-diketiminato and novel linked bis(beta-diketiminato) ligands: Synthesis, structural characterization and catalytic application in epoxide/CO2-copolymerization

Mesityl substituted beta-diketiminato lanthanum and yttrium complexes [(BDI)Ln{N(SiRMe2)}2] (BDI = ArNC(Me)CHC(Me)NAr, Ar = 2,4,6-Me3C6H2, Ln = La, R = Me (1), H (2a); Ln = Y, R = H (2b)) can be prepared via facile amine elimination starting from [La{N(SiMe3)2}3] and [Ln{N(SiHMe 2)2}3(THF)2] (Ln = Y, La), respectively. The X-ray crystal structure analysis of 1 revealed a distorted tetrahedral geometry around lanthanum with a eta2-bound beta-diketiminato ligand. A series of novel ethylene- and cyclohexyl-linked bis(beta-diketiminato) ligands [C2H4(BDI Ar)2]H2 and [Cy(BDIAr) 2]H2 [Ar = Mes (=2,4,6-Me3C6H 2), DEP (=2,6-Et2C6H3), DIPP (=2,6-i-Pr2C6H3)] were synthesized in a two step condensation procedure. The corresponding bis(beta-diketiminato) yttrium and lanthanum complexes were obtained via amine elimination. The X-ray crystal structure analysis of the ethylene-bridged bis(beta-diketiminato) complex [{C2H4(BDIMes)2}YN(SiMe 3)2] (3b) and cyclohexyl-bridged complexes [{Cy(BDI Mes)2}LaN(SiHMe2)2] (7) and [{Cy(BDIDEP)2}LaN(SiMe3)2] (8) revealed a distorted square pyramidal coordination geometry around the rare earth metal, in which the amido ligand occupies the apical position and the two linked beta-diketiminato moieties form the basis. The geometry of the bis(beta-diketiminato) ligands depends significantly on the linker unit. While complexes with an ethylene-linked ligand adopt a cisoid arrangement of the two aromatic substituents, complexes with cyclohexyl linker adopt a transoid arrangement. Either one (3b) or both (7, 8) of the beta-diketiminato moieties are tilted out of the eta2 coordination mode, resulting in close Ln?C contacts. The beta-diketiminato and linked bis(beta- diketiminato) complexes were moderately active in the copolymerization of cyclohexene oxide with CO2. A maximum of 92% carbonate linkages were obtained using the ethylene-bridged bis(beta-diketiminato) complex [{C 2H4(BDIMes)2}LaN(SiHMe 2)2] (4).

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Ready available chiral azapyridinomacrocycles n-oxides; First results as lewis base catalysts in asymmetric allylation of p-nitrobenzaldehyde

We report here the straightforward synthesis of the first series of enantiomerically pure azapyridinomacrocycles N-oxides containing a cyclohexyl chiral moiety. These compounds were readily obtained in good overall yields by a convergent synthesis using natural amino acids as starting building blocks and macrocyclisation as the key step. This method is rapid, efficient and suitable for the introduction of various substituents at the macrocyclic skeleton. Finally, the compounds were tested as organocatalysts for the enantioselective allylation of p-nitrobenzaldehyde with allyltrichlorosilane.

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Synthesis and characterization of dinuclear copper(II) complexes, [Cu 2([20]-DCHDC)(La)2] (La = N 3-, NCS- or S2O3 2-) with tetraazadiphenol macrocyclic ligand having cyclohexane rings

The chiral dinuclear tetraazadiphenol macrocyclic copper(II) complexes [Cu2([20]-DCHDC)(La)2] {H2[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,04,9,1 12,16,019,24]ditriacontane-2,10,12,14,16(32),17,27(31),28, 30-decane-31,32-diol; La = N3- (II), NCS – (IV) or S2O32- (V)} has been synthesized and structurally characterized by elemental analysis, conductance, electronic and IR spectra as well as FAB-MS method. Crystal structure of [Cu2([20]-DCHDC)(N3)2] ?2CH3OH (III) determined by X-ray crystallography reveal the two square pyramidal copper centers bridged by the two phenoxide oxygen atoms, with large Cu-O-Cu angles {100.88(10)}.

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Synthesis and characterisation of asymmetrically bridged calix[4]arene and tetrathiacalix[4]arene mono amido crown derivatives

The synthesis of asymmetrically bridged calix[4]arene and tetrathiacalix[4]arene amido crown derivatives has been achieved by the aminolysis of distal diester derivatives of calix[4]arene and tetrathiacalix[4]arene with 1,2-diaminopropane or 1,2-diaminocyclohexane (stereoisomeric mixture, mainly trans). The title compounds have been characterised by detailed analysis of their NMR spectra. The assignment of NMR signals and stereo differentiation in the amido crown ring formation has been studied using a chiral shift reagent.

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