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In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials.

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

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Complexes of rhodium and iridium of the types MX3L, MX(CO)2L and MX3(CO)L (X = halide) containing multidentate N-heterocycles (L), 2,6-bis(benzimidazolyl)pyridine (bBzlH2py) and 2,6-bis(N-methyl-benzimidazolyl)pyridine (bBzlMe2py) have been prepared and characterized by IR, electronic and 1H and 13C NMR spectral data. RhX(CO)2L, on treatment with alcoholic solvents or DMF undergoes reversible decarbonylation to produce RhXL·2H2O. Passage of NO or O2 through the carbonyl suspended in hot 2-methoxyethanol releases CO2. Copyright

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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 invention discloses a symmetric benzimidazole ruthenium complex and its preparation method and belongs to the technical field of synthetic chemistry. According to the preparation method, 2,4,6-trismesitylene and triethyl phosphate are used as starting materials, a fixed ligand is synthesized by a two-step method, and the fixed ligand finally reacts with ruthenium trihydrate under the microwave condition so as to synthesize the target product. The synthesized symmetric benzimidazole ruthenium complex has excellent stability and optical and electrochemical properties. Through covalent bond effect between symmetric phosphate groups at two ends of the molecule and the surface of a conductive substrate such as ITO and the like, the symmetric benzimidazole ruthenium complex molecule is fixed to the conductive substrate and layer-by-layer self-assembly is realized. The symmetric benzimidazole ruthenium complex is an excellent photosensitizer. In addition, the designed synthesis process of the symmetric benzimidazole ruthenium complex is simple, costs are low, and the microwave-assisted synthesis technology is rapid and efficient.

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

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Homo- and heteroleptic bis-tridentate ruthenium(ii) and osmium(ii) complexes of compositions [(tpy-PhCH3)Ru(tpy-HImzPh 3)](ClO4)2 (1), [(H2pbbzim)Ru(tpy- HImzPh3)] (ClO4)2 (2) and [M(tpy-HImzPh 3)2](ClO4)2 [M = RuII (3) and OsII (4)], where tpy-PhCH3 = p-methylphenyl terpyridine, H2pbbzim = 2,6-bis(benzimidazole-2-yl)pyridine and tpy-HImzPh3 = 4?-[4-(4,5-diphenyl-1H-imidazol-2-yl)-phenyl]-[2, 2?:6?,2??]terpyridine, have been synthesized and characterized by using standard analytical and spectroscopic techniques. These compounds were designed to increase the room temperature excited-state lifetimes of bisterpyridine-type ruthenium(ii) and osmium(ii) complexes. The X-ray crystal structures of two homoleptic complexes 3 and 4 have been determined and show that both the compounds crystallized in orthorhombic form with space group Fddd. The photophysical and redox properties of the complexes have been thoroughly investigated. All the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 6-35 ns. The complexes are found to undergo one reversible oxidation in the positive potential window (0 to +1.6 V) and one irreversible and two successive quasi-reversible reductions in the negative potential window (0 to -2.0 V). The influence of solvents on the photophysical properties of the complexes has also been investigated in detail. 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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[Ru(bzimpy)2]Cl2, where bzimpy is 2,6-bis(benzimidazol-2-yl) pyridine was synthesized and characterized by ESI-MS, UV-Visible, 1H NMR and fluorescence spectra. Absorption titration and thermal denaturation experiments indicate that the complex binds to DNA with moderate strength. Viscosity measurement shows that the mode of binding could be surface binding. Fluorescence study shows that the fluorescence intensity of the complex decreases with increasing concentrations of DNA, which is due to the photoelectron transfer from guanine base to 3MLCT of the complex. Photoexcitation of the complex in the MLCT region in the presence of plasmid DNA has been found to give rise to nicking of DNA.

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

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Abstract 2,6-Di(1H-benzo[d]imidazol-2-yl)pyridine (DBIP) was synthesized. The single-crystal structure of DBIP was resolved. DBIP-based OLED was fabricated. The electroluminescence for the device corresponds to a pure white emission. In addition, thermal stability, UV-vis, photoluminescence and electrochemical behaviors of DBIP were investigated as well.

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

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Mono-cationic Ru(II)-complexes [Ru(L)X(CH3CN)2]?X 1?4 (1, L = 2,6-bis(benzimidazol-2-yl) pyridine (L1), X = Cl; 2, L = L1, X = OTf; 3, L = 2-(N-benzyl-benzimidazole-2-yl)-6-(benzimidazole-2-yl)pyridine (L2), X = Cl; 4, L = 2,6-bis(N-benzyl-benzimidazole-2-yl)pyridine (L3), X = Cl) were prepared and fully characterized. The two acetonitrile ligands of each complex are coordinated to the metal center cis to each other. Complex 2 was also structurally characterized by X-ray crystallography. It was found that complexes 1?4 can catalyze the acceptorless dehydrogenation of primary alcohols to corresponding carboxylic acids and H2in the basic aqueous solution, and the reactivity follows the order 1 = 2 > 4 > 3. Furthermore, complexes 1 or 2 can efficiently catalyze the conversion of various primary alcohols to carboxylic acid in good yields (72%?98%) and high selectivity in an alcohol/CsOH system (1/1, mol/mol). Using an excess amount of alcohol to CsOH results in the formation of the carboxylic acid in higher yield (up to 100%, based on CsOH) and higher turnover numbers (TON ? 10000) accompanied by the H2evolution. Complexes 1 and 2 can act as a new class of phosphine- and N-heterocycle carbene free Ru(II) complexes for efficient conversion of primary alcohols to carboxylic acids and H2in a homogeneous system.

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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 series of bis(benzimidazole)-based cobalt(II) dichloride complexes containing a range of different central donors has been synthesized and characterized. The nature of the central donor affects the binding of the ligand to the cobalt centre and determines the coordination geometry of the metal complexes. All complexes have been shown to catalyse the polymerization of butadiene, in combination with MAO as the co-catalyst, to give cis-1,4-polybutadiene with high selectivity. The nature of the central donor has a marked influence on the polymerization activity of the catalysts, but does not affect the polymer microstructure. The addition of PPh3 generally increases the polymerization activity of these cobalt catalysts and results in predominantly (60-70%) 1,2-vinyl-polybutadiene. The Royal Society of Chemistry 2010.

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

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Polymer supported and unsupported oxovanadium(IV) complexes with 2,6-bis(benzimidazolyl)pyridine were synthesized and characterized by elemental analyses, molar conductance, magnetic moment measurements, electronic, IR, ESR spectral studies, LC?MS and thermogravimetric analysis. Based on the results, an octahedral geometry was intended around V(IV) complexes. Polymer-anchored V(IV) complex catalyzed the oxidation of benzyl alcohols in acetonitrile with O2 as an oxidant. Several parameters were differed to optimize the reaction conditions. Under the optimized reaction conditions, benzyl alcohol oxidation confirmed 96% conversion with 100% selectivity towards benzaldehyde. The developed catalyst revealed excellent benzyl alcohol oxidation at moderate temperature in presence of oxygen making the reaction simpler and environmentally benign. The polymer anchored V(IV) complex showed excellent recyclability as compared to its unsupported analogue. Graphical Abstract: [Figure not available: see fulltext.].

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

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In present work, the electrical properties and illumination effects were investigated for the silicon based photodetector with organic Ru(II) complexes interfacial layer. The current-voltage (I-V) and capacitance/conductance-voltage (C/G-V) measurements were analyzed to determine electrical and photoelectrical properties under dark and different solar light intensity conditions. The reverse bias current values under light conditions were higher than dark conditions, and this situation demonstrates that the fabricated device displays a photoconducting behavior. Besides, some crucial electrical parameters such as series resistance, barrier height and ideality factor values of prepared device were calculated by using current-voltage measurements. The ideality factor and barrier height values of fabricated device were calculated as 9.42 and 0.59 for dark condition. Besides to these experiments, transient photocurrent and photo-capacitance/conductance were also investigated under different light conditions. It was determined from transient measurements that the fabricated device has a high sensitivity to light. The photoresponse of the diode was determined to be around 4479 ± 1.9 under 100 mW/cm2 illumination. The examined C/G-V characteristics of the fabricated device strongly depend on voltage and frequency. The analyzed results suggest that the fabricated Al/Ru(II) complexes/p-Si/Al device can be used in rapidly developing optoelectronic applications, especially for the organic materials-based photodetector technology.

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