查看更多>>摘要：Herein, we report the synthesis, characterization and combined structural and full computational analysis of noncovalent interactions in a new hydrazine ligand and its two chlorido-and endo-nitrito-rhenium(I) tricarbonyl complexes. The analysis of crystal structures has been accompanied by comprehensive computational studies of the noncovalent interactions utilizing the quantum theory of atoms in molecules (QTAIM), natural bond orbitals (NBO), independent gradient model (IGM), and electron localization function (ELF) to shed light on the nature of the interactions. On the other hand, comprehensive energy decomposition analysis (EDA) by extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) scheme in a series of crystallographically retrieved dimers of the complexes was done to unveil the physical origin of these interactions and the factors affecting the interaction strength. In case of the Re-& UKappa;1-nitrito complex, the Interacting Quantum Atoms (IQA) scheme was used for detailed analysis of the interesting intramolecular Re-& UKappa;1-endo-ONO(lone pair)...pi* (C---O) interaction in the nitrito complex.
查看更多>>摘要：The synthesis of five 1,10-phenanthroline-based ligands (ligands A -E), where a pyridinone group is grafted onto a 1,10-phenanthroline backbone through various linkers is described. From these compounds and ligand F (a 2,2'- bipyridine backbone fused with a NH-CO motif), two monomeric octahedral complexes formulated as [Ti(1)2(A)] and [Ti(1)2(F)] (1 is 6,6 & PRIME;-diphenyl-2,2'-biphenolato) are obtained. The X-ray crystal structures attested the formation of hydrogen bonded supramolecular dimers in the solid state for both complexes. Colorimetric cell viability assays (MTT) performed on human gastric adenocarcinoma cells (AGS) have permitted to determine IC50 around 20 mu M for phenanthrolines A -C whereas compound F was non-toxic. Owing their insolubility, the cytotoxic activities of the two Ti-complexes were not measured. Docking experiments conducted with [Ti(1)2(A)] and [Ti(1)2(F)] evidenced major clashes within the MST2 kinase binding pocket while the free ligands have a shape fitting with the size of this enzyme pocket.
查看更多>>摘要：Isocyanide ligands RNC (R = 4-(MeO)C6H4-, PhCH2) react smoothly with trans-[Pt(mu-Cl)Cl(PPh3)](2) to afford trans-[PtCl2(PPh3)(CNR)] complexes, which are promptly converted, in solution, to the corresponding cis isomers. The obtained derivatives react with N,N-dialkylamines to afford the corresponding N-acyclic carbene (NAC) addition products. When alicyclic N,N-dialkylamine (R2NH, R=ethyl, benzyl) were used, only the expected neutral dichlorocarbene product cis-[PtCl2(PPh3)(R2NCN(H)R)] were obtained in high yields, while when cyclic amines (R'2N) over capH were used (morpholine, piperidine, pyrrolidine), variable amounts of ionic [PtCl(PPh3) ((R' 2N) over capH)((R' 2N) over cap CN(H)R)]Cl were observed, arising from the substitution of a residual chlorido ligand by the used amine. The amount of the ionic derivative observed depends on the amine nucleophilicity.
Chiaverini, LorenzoMarzo, TizianoLa Mendola, Diego
8页
查看更多>>摘要：Inorganic chemistry holds a central role in the management of several diseases both from the diagnostic as well as from the therapeutic point of view. Various platinum drugs are approved at the global or local level for cancer treatment while other transition metals are used for different therapeutic applications or diagnosis. However, even semimetals i.e., the elements which lie on the diagonal connecting boron to polonium are being used in medicine where some compounds with therapeutic properties have been approved by the Food and drugs Administration (FDA) and the European Medicinal Agency (EMA). In the last decades growing attention has been devoted towards tellurium for the preparation of pharmacologically active agents. In this context, Ammonium trichloro(dioxoethylene-O,O ')tellurate (AS101) emerged as a reference tellurium-based compound. This Te(IV) compound is well tolerated in animal models and its peculiar reactivity towards thiol residues of enzymes such as cysteine proteases is at the heart of its pharmacological effects. Actually, AS101 entered several clinical trials due to its good tolerability. In this mini-review the main chemical and biological aspects of this promising metalloidbased drug are briefly summarized and the outcomes as well as future perspectives for the design of improved Tebased compounds are discussed.
查看更多>>摘要：A new 3D metal-organic framework (MOF) with formula [Mn-4(NDC)(2)(bb)(4)] (1) (H2NDC = 1,4-naph-thalenedicarboxylic acid and bb = 4,4'- bis(imidazolyl) biphenyl), has been prepared and characterized using FTIR spectroscopy and single crystal X-ray. The single crystal X-ray analysis reveals that 1 comprises of 6 -connected mab-type network with (44.610.8) point symbol. The photocatalytic properties of 1 to photodegrade aromatic dyes reveals that it could effectively photodegrade dyes viz. Rhodamine B (Rh B), Chrome Blue (CB), and methylene blue (MB). Moreover, the active species involved in the degradation of Rh B has been assessed using trapping experiments and band gap calculation has been performed to establish the plausible photo -catalytic mechanism.
Munnik, Brandon L.Kaschula, Catherine H.Watson, Daniel J.Wiesner, Lubbe...
6页
查看更多>>摘要：Six half-sandwich complexes of iridium (III), rhodium (III), and ruthenium (II) (C1-C6) bearing the N,N'-chelated ligand 2-(2-pyridyl)benzimidazole (L) were synthesized and characterized, three of which, bearing the iodido ligand are new. The complexes were isolated as yellow or orange solids in moderate to good yields. The com-plexes were tested for their ability to catalyse the hydrogenation of NAD+ to NADH at pH 7 at 37 degrees C. The iridium complexes (C1 and C2) were found to perform the best with NADH yields of up to 74% after one hour. All of the complexes and the ligand were screened for their ability to inhibit growth of the drug-sensitive strain of malaria-causing parasite Plasmodium falciparum, NF54. The complexes containing the rhodium (III) metal centre had the highest activity with the IC50 values for the chlorido (C3) and iodido (C4) complexes determined to be 11.4 mu M and 9.65 mu M respectively. Both complexes performed better than the ligand (IC50 = 55.9 mu M). Complexes bearing the iodido ligand were found to be favourable in both the catalysis as well as the antimalarial assays.
查看更多>>摘要：A series of metal-rich clusters of group 9 containing boride or borylene units have been isolated and structurally characterized. The thermolysis reaction of arachno-[IrCp*H-2(B3H7)] (I) with [Ru-3(CO)(12)] allowed to isolate the mu 5-boride nido-[(IrCp*){Ru(CO)(2)}{Ru(CO)(3)}(3)(mu-H)(5)B2H2(mu(5)-B)] (1) and the tetrametallic cluster [(IrCp*)(2){Ru (CO)(2)}{Ru(CO)(3)}(mu-CO)(2)(mu(3)-BH)] (2) with a mu(3)-coordinated triply-bridged borylene moiety. The geometry of cluster 1 can be derived from an eight-vertex closo-dodecadeltahedron by removal of one five-connected vertex followed by capping of a Ru(CO)(3) moiety. The borylene moiety (BH) of cluster 2 is connected in a mu(3)-fashion to the deltahedral face of a tetrametallic tetrahedron (Ir2Ru2). To synthesize the Mn analogue of 2, thermolysis reaction with [Mn-2(CO)(10)] was carried out, that afforded the trimetallic tetrahedral borylene [(IrCp*)(2){MnH (CO)(3)}(mu-CO)(2)(mu(3)-BH)] (3) along with the known face-fused boride [{Ir(CO)(2)}(3)(IrCp*)3(mu(3)-CO)(mu-CO)(mu(5)-BH)] (4). Clusters 2 and 3 are the first triply-bridged borylenes having an Ir metal atom in the core. All these clusters were characterized by NMR (H-1, B-11 and C-13), infrared (IR) spectroscopies and mass spectrometry. The structure of cluster 1 was confirmed by X-ray diffraction analysis. In addition, density functional theory (DFT) calculations were conducted to interpret and study the nature of bonding and electronic structure of cluster 1.
查看更多>>摘要：This study presents a combined experimental and computational investigation on a dinuclear Cu(II) complex containing 3-[2-[(ethanol amino)ethyl]imino]-2-butanoneoxime ligand (L). The compound [CuL]2(NO3)2 was studied by IR, UV-Vis spectroscopy, thermogravimetry analysis, and molar conductance measurements. The square-pyramid geometry of the complex was confirmed by both the density functional theory level (DFT) calculation and X-ray crystallography. The complex was halochromic, and its halochromism was studied in an aqueous solution. The original green complex displayed reversible color change to blue in alkaline and colorless in acidic solutions. The pH effect on the visible absorption spectrum of the complex was studied that functions as pH-induced "off-on-off" switches triggered by the protonation and loss of the ligand L in acidic medium and deprotonation of ligand in a basic aqueous solution. Further computational analysis of the electronic structure of the complex was carried out to gain a deeper insight into the properties associated with molecular orbitals. Its electronic spectrum was analyzed, and bands were assigned through the time-dependent density functional theory level (TDDFT) calculation.
查看更多>>摘要：Highly sensitive and selective fluorescence sensing of antibiotics and heavy metal ions are extremely vital to safeguard human health. Two new water-stable ternary coordination polymers (CPs), {[Cd(NPTA)(L)]middot1.75H(2)O}(n) (1) and [Co-1.5(BTC)(L)](n) (2) (H(2)NPTA = 3-nitrophthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid, and L = 1,5-bis(benzimidazole-2-yl)pentane) were prepared through the hydrothermal process. 1 features a 1D zigzag infinite chain which is linked into a 2D network via pi-pi stacking interactions, while 2 shows a 2D 3,4L35 layer and can be further extended into a 3D supramolecular framework by hydrogen-bonding interactions. The two CPs display superior thermal and chemical stability in a wide pH range from 3 to 12. Furthermore, both 1 and 2 can be as the dual-responsive probes for selective sensing of enrofloxacin (ENR) and Al3+ ions with reusability.
查看更多>>摘要：Establishing a simple and rapid method for the detection of vanillin is necessary and significant. Herein, we synthesized a new 3D luminescent coordination polymer (LCP) [Cd(4-bmnpd)(BA)](1) {4-bmnpd = N,N'-bis(4-methylpyridine-4-yl)-2,6-naphthalene dicarboxylamide, H2BA = 2[(4-carboxymethyl phenoxy) benzoic acid]} with a semi-rigid bis-pyridine-bis-amide and dicarboxylate mixed ligands under solvothermal condition. X-ray diffraction analysis revealed that 1 is a 5-connected 3D framework structure. The effect of solvents and pH on the luminescence intensity of 1 was investigated. LCP 1 was stable and the luminescence intensity almost unchanged in different solvents as well as in the pH range of 3-11. Fluorescence sensing studies showed that LCP 1 can detect vanillin by fluorescence quenching and has good anti-interference properties toward the substances commonly found in infant formula. The limit of detection of vanillin was as low as 1.41 mu M. The fluorescence quenching mechanism of LCP 1 was analyzed in detail. In addition, we developed cheap paper-based sensor for visual recognition detection of vanillin.
NSTL
Elsevier