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N-substituted metal-coordinated cross-linking polybenzimidazole pyridine sulfone, as novel class of high-performance functional polymers, has been obtained by the coordination of N-substituted polybenzimidazole pyridine sulfone (Py-N-PBIS) ligand with varying content of metallic ion (Co2+, Ni2+, Zn2+). The structures of the polymers are characterized by means of fourier transform infrared spectroscopy (FT-IR) and 1H nuclear magnetic resonance (1H NMR) spectroscopy, the results show good agreement with the proposed structures. Thermogravimetric analysis measurements exhibit that the metal coordination polymers possess good thermal stability with high thermal decomposition temperature (thermally stable up to 405?510C). More importantly, the thermal decomposition temperature of Py-N-PBIS-(Co2+, Ni2+, Zn2+) can be nondestructively detected by taking advantage of the fluorescence quenching effect of metal coordination to 2,6-Bis(2-benzimidazolyl)pyridine structure.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Under microwave assistance, 2,6-bis(benzimidazolyl)-pyridine has been concisely synthesized and further productively converted to the functional molecule BMBP via accessible N-alkylation reaction. For the introduction of alkoxyalkyl chain, this original substance BMBP with better solubility in water exhibits specific fluorescence response toward Zn2+ from colourless to blue in aqueous solution. A sequential detection for picric acid (PA) can be conducted in this following system, showing the high selectivity and sensitivity of quenching over other analogues. On the basis of the comparison with the control BMBB, a cascade sensing mechanism has been disclosed to accelerate the recognition of structure-property relationship, which is fully supported by LC-MS, 1H NMR, lifetime measurement and theoretical calculation. Noteworthily, BMBP is also readily available for practical application not only in quantitative determination of Zn2+ and PA in real water samples, but also in visible detection of two analytes in multiple forms on paper test strips, offering convenient process for low-cost, portable and versatile sensing device.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Lanthanide(III) coordination compounds are employed in several fundamental and applied research fields such as organic synthesis, bioinorganic chemistry, optical and magnetic imaging, catalysis, environment and geochemistry. All these applications have been favoured by the recent developments of a detailed knowledge of fundamental properties (electronic, spectroscopic, thermodynamic, magnetic, structural) of elements, ions and their compounds.Ln3+ are hard acids and present strong affinity for charged ligands or neutral O- and N-donors, as indicated by a wide number of papers concerning formation of their complexes in solution. These studies allowed one to gain information on the complex stabilities, the metal-ion selectivity of a given ligand, the influence of the solvent on the nature and stability of the species in solution. Most of the above studies deal with aqueous solutions, while studies in non-aqueous media are less common. Despite more limited, investigations in aprotic solvents are particularly interesting as they allow one to extend the knowledge on the coordination chemistry of lanthanide(III), disclosing metal-ligand interactions not easily accessible in water due to ligand protonation equilibria, Ln(III) hydrolysis and strong hydration of the cations, which hampers interactions with neutral donors.This review analyzes a wide number of thermodynamic studies concerning formation of lanthanide(III) complexes with selected, simple neutral N-donors (amines, pyridines), O-donors (crown ethers, aza-crown ethers and cryptands) and charged inorganic ligands (halides, thiocyanate, nitrate, perchlorate, triflate) in non-aqueous solvents. The main aim of the review is to face the basic question of what are the factors governing the complex stability and selectivity within the lanthanide series and how are they influenced by different coordinating media. Fundamental properties of Ln ions, such as ionic radii, common oxidation states and structural aspects of their solvates are as well analyzed.Several points emerged from a critical analysis of the papers reviewed:. i)Ln3+ salts used in thermodynamic studies in poor coordinating solvents are often not completely dissociated and, in this case, the data obtained reflect multiple simultaneous equilibria in solution. Comparisons between thermodynamic results in poor and high solvating media must be therefore regarded with caution as they may refer to different reacting metal-species, hence, to different metal-ligand equilibria.ii)High solvating aprotic media can be considered as ideal for thermodynamic studies since lanthanide(III) is only present as Ln(solv)n3+species. However, in this case, the strong solvation of Ln3+ ions hinders complex formations with weak or relatively weak donors.iii)Solvation of lanthanide(III) cations in non-aqueous solutions is generally a major factor in determining the complex stabilities which, for the different kinds of ligands examined, follow the general trend: PC>AN>MeOH>DMF>DMSO.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A neutral hexacoordinate silicon complex containing two 2,6-bis(benzimidazol-2?-yl)pyridine (bzimpy) ligands has been synthesized and explored as a potential electron transport layer and electroluminescent layer in organic electronic devices. The air and water stable complex is fluorescent in solution with a lambdamax = 510 nm and a QY = 57%. Thin films grown via thermal evaporation also fluoresce and possess an average electron mobility of 6.3 × 10-5 cm2 V-1 s-1. An ITO/Si(bzimpy)2/Al device exhibits electroluminescence with lambdamax = 560 nm.

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Palladium/carbon catalyst regeneration and mechanical application method

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The design of molecule-based systems displaying tuneable optical and/or magnetic properties under external stimuli has received a great deal of attention in the past few years. This interest is driven by the potential applications in high-performance molecule-based electronics in the areas of recording media, switches, sensors, and displays. As an example, three-dimensional Fe/Co Prussian blue compounds exhibit a concomitant change in magnetic and optical properties due to a temperature- or light-induced metal-to-metal electron transfer. The foregoing remarkable properties in Prussian blues prompted us to design soluble molecular fragments of these coordination networks through a rational building-block approach in order to mimic their properties on a single molecule. With a judicious choice of the ligands for the iron and cobalt molecular precursors, we prepared a dinuclear cyanido-bridged Fe/Co complex that exhibits an unexpected temperature-dependent spin crossover in the solid state while an intramolecular electron transfer triggered by protonation is observed in solution.

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Palladium/carbon catalyst regeneration and mechanical application method

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A series of luminescent Zn(II) and Cd(II) complexes have been prepared based on three different pi-conjugated ligands, 2-(2-pyridyl)-imidazole (HL1), 2-(2-pyridyl)-benzimidazole (HL2) and 2,6-bis(benzimidazol-2yl)-pyridine (H2L3). The PL spectra of the ligands exhibit a bathochromic shift in agreement with the extended pi-conjugation of the ligand. The spectra of the complexes with the ligands follow the same rule. The structures of Zn(L2) 2H2O (5), [Cd(L2)2(H2O)2] ? 2DMSO (6), Zn(HL3)2 (9) and Cd(HL3)2 (10) have been established by X-ray crystallography. The structure of 5 can be best described as a square pyramid. The coordination geometries of 6, 9 and 10 can be described as distorted octahedrons. In the solid state and in DMSO, these complexes show emission maxima in the blue region. The complexes have a bathochromic shift of the emission energy in sharp contrast to the free ligands. They display blue luminescence and have high luminescence quantum efficiency. A theoretical study reveals that the emissions are assigned to intraligand transitions of the deprotonated L2 and HL3 ligands, and the metal ions in the complexes play a key role in stabilizing the ligand and promoting the luminescence, which is consistent with the experimental results.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The new gold(iii) complexes: [Au{2-(2?-pyridyl)imidazolate}Cl 2] and [Au{2,6-bis(2?-benzimidazolate)pyridine}(OCOCH 3)] and the mono- and binuclear gold(i) complexes: [Au{2-(2?-pyridyl)imidazole}(PPh3)](PF6), [Au(2-phenylimidazolate)(DAPTA)] (DAPTA = 3,7-diacetyl-1,3,7-triaza-5- phosphabicyclo[3.3.1]nonane), [(PPh3Au)2(2-R-imidazolate)] (PF6) (R = 2-C5H4N, Ph) have been synthesized and characterized. The structure of the [(PPh3Au)2{2- (2?-pyridyl)imidazolate)](PF6) complex was also characterized by X-ray crystallography. The antiproliferative properties of the complexes were assayed against human ovarian carcinoma cell lines, either sensitive (A2780) or resistant to cisplatin (A2780cisR), human mammary carcinoma cells (MCF7) and non-tumorigenic human kidney (HEK293) cells. Most of the studied compounds showed important cytotoxic effects. Interestingly, the compounds containing the 2-(2?-pyridyl)imidazolate ligand showed selectivity towards cancer cells with respect to the non-tumorigenic ones, with the dinuclear compound [(PPh 3Au)2{2-(2?-pyridyl)imidazolate)](PF6) being the most active. Some compounds were also screened for their inhibitory effect of the zinc-finger protein PARP-1, essential for DNA repair and relevant to the mechanisms of cancer cell resistance to cisplatin. Interaction studies of the compounds with the model protein ubiquitin were undertaken by electrospray ionization mass spectrometry (ESI MS). The results are discussed in relation to the putative mechanisms of action of the cytotoxic gold compounds. The Royal Society of Chemistry 2012.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A potent superoxide dismutase mimic, MnII(HL)2 [H2L = 2,6-bis(benzimidazol-2-yl)pyridine] has been synthesised and characterised by its crystal structure determination and EPR spectroscopy. Copyright 1996 by the Royal Society of Chemistry.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The structure of [Zn(C19H12N5)2], which is monomeric and consists of neutral Zn(bbip-H)2 entities [bbip-H is the anionic form of bis(benzimidazolyl)pyridine, formed by the loss of one H atom], has been solved from a racemic twin. The Zn atom lies at a site with imposed 222 symmetry and the bbip-H ligand has imposed twofold symmetry. The imidazolyl H atom is disordered over two symmetry-related positions, thus raising the molecular symmetry as required by the space group. The angle between the planes of the two coordinated bbip-H ligands is 84.6 (3), so defining a distorted octahedral environment around the metal atom.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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We have recorded the powder EPR-spectra of some near octahedral iron(III) complexes with tridentate ligands donors and analyzed their spectra with simple ligand field analysis and for some cases with the angular overlap model (AOM). We have determined the electron paramagnetic resonance (EPR) characteristic of bis 1,4,7-triazacyclonane iron(III)chloride at 4 K and found that it was similar to the characteristics of the so-called `highly anisotropic low spin’ complexes. We have recorded the powder spectra of bis (2,6-bis(benzimidazoly-2-yl)pyridine) iron(III) perchlorate and made an AOM-analyses of the structural similar complex bis-(2,6 (N-carbamoyl)-pyridine) iron(III). With a combination of ligand field analyses and AOM, we could determine the pi-donor properties of these ligands. The same approach have been used to determine the pi-donor properties of the hydroperoxo ligand. Finally we have recorded the powder EPR-spectrum of [Fe(CN)6]3- doped in K3[Co(CN)6] and [Co(NH3)6][Co(CN)6] at 4 and 100 K and in water at 4 K. The spectra are interpreted as the effect of a dynamic Jahn-Teller distortion.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method