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Effect of Coordination Geometry on Magnetic Properties in a Series of Cobalt(II) Complexes and Structural Transformation in Mother Liquor

The three Co(II) complexes [Co(bbp)2][Co(NCS)4]¡¤4DMF (1), [Co(bbp)(NCS)2(DMF)]¡¤2DMF (2), and [Co(bbp)(NCS)2] (3) have been synthesized and characterized by single-crystal X-ray diffraction, magnetic, and various spectroscopic techniques. Complexes 1 and 3 are obtained by the reaction of Co(NCS)2 with 2,6-bis(1H-benzo[d]imidazol-2-yl)pyridine (bbp), and complex 1 undergoes a structural transformation to form complex 2. A single-crystal X-ray study revealed that complex 1 is comprised of two Co(II) centers, a cationic octahedral Co(II) unit and an anionic tetrahedral Co(II) unit, while the Co(II) ion is in a distorted-octahedral environment in 2. Moreover, in complex 3, the Co(II) ion is in a distorted-square-pyramidal geometry. The effect of coordination geometry on the magnetic properties was studied by both static and dynamic magnetic measurements. Direct current (dc) magnetic susceptibility measurements showed that all of the Co(II) ions are in high-spin state in these complexes. Alternating current (ac) magnetic susceptibility measurements indicated that complexes 2 and 3 display slow relaxation of magnetization in an external dc magnetic field, while complex 1 displayed no such property. EPR experiments and theoretical calculations were consistent with the above findings.

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

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Heteroleptic neutral Ru(II) complexes based photodiodes

The two complexes Ru(II) containing 2,6-bis(benzimidazol-2-yl)pyridine and 2-pyridine and 2-quinoline carboxylates were synthesized to fabricate organic photodiodes. The electrical properties of Au/Ru(II) complex (I)/n?Si/Al and Au/Ru(II)complex (II)/n?Si/Al diodes were investigated by current-voltage and capacitance-voltage measurements. The fabricated devices give a high rectification behavior with rectification ratio of 2.4 ¡Á104 ?2.1 ¡Á103 at ¡À4 V. The diodes exhibited a high photoconductivity based on trap levels within band gap. The series resistance and barrier height were calculated from (C?V) measurements and compared to other of (I?V). The obtained results indicate that the prepared photodiodes can be used as photosensor for optoelectronic applications.

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

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Spin-Transition Behaviour of Transition Metal Complexes with 2,6-bis-(Benzimidazol-2′-yl)-pyridine Induced by Deprotonation of the Complex

2,6-bis-(Benzimidazol-2′-yl)-pyridine (bzimpy = H2L) acts as a bidentate ligand when combining with transition metal ions.The complexes (ClO4)2 (M = Fe(2+), Mn(2+), Zn(2+), Co(2+), and Ni(2+)) were obtained as solids.The protonation constants (log K) for the ligand and the complexes were evaluated in 30:70 (v/v) H2O:EtOH at 293 K and at constant ionic strength of 0.12M KCl.Coordination of the ligand to the metal ions leads to an increase of acidity of the imino-hydrogen of the benzimidazole group of the ligand as a function of the complex stability.Deprotonation leads to a spin-state transition (intermediate spin-state –> low-spin) of the iron(II)-complex, followed by a shift of the metal-to-ligand charge transfer band (MLCT) to lower energies (lambdamax = 563 to 580 nm).The d-d absorption bands are found to shift to higher energies and the low-spin isomer is favoured at room temperature.An opposite shift of the MLCT band (lambdamax = 563 to 557 nm) is observed when HClO4 is added to the complex solution, rendering the high-spin state of the complex more favourable. – Keywords. 2,6-bis-(Benzimidazol-2′-yl)-pyridine; Spin-Crossover behaviour; Deprotonation; Transition metal complexes.

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

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Molecular design of a proton-induced molecular switch based on rod-shaped Ru dinuclear complexes with bis-tridentate 2,6-bis(benzimidazol-2-yl)pyridine derivatives

New dinuclear Ru complexes of bis-tridentate 2,6-bis(benzimidazol-2-yl) pyridine derivatives, [Ru2(terpy)2(H4Ln)]4+ (terpy = 2,2?:6?,2?-terpyridine, n = 0-2), have been synthesized. The Ru complexes act as tetrabasic acids, in which N-H protons on benzimidazole moieties are responsible for a deprotonation site. Both the absorption spectra and oxidation potentials are strongly dependent on the solution pH, which leads to the basis of a proton-induced molecular switch. The dinuclear Ru complexes bridged by bis-tridentate bis{2,6-bis(benzimidazol-2-yl) pyridine} show a lower Ru(II/III) oxidation potential but almost similar MLCT absorption maxima, compared to the corresponding dinuclear Ru complexes with “back-to-back” bis-2,2?:6?,2-terpyridine bridging ligands. These results indicate that the bis-tridentate bis{2,6-bis(benzimidazol-2-yl) pyridine} ligand has a stronger sigma/pi donor property and a weaker pi-acceptor property than the bis-2,2?:6?,2?-terpyridine bridging ligand. The solubility of Ru complexes in solution is progressively decreased with increasing number of phenyl group in the bridging ligand, and therefore it becomes difficult to study the change of chemical properties for external stimuli such as pH change. Immobilization of complexes on a solid surface is one of the approaches to overcome their low solubility. The [Ru 2(bpbbip)2- (H4L0)]4+ complex with phosphonate groups (bpbbip = 2,6-bis(1-(4-diphosphonyl)butylbenzimidazol-2-yl)pyridine) was successfully immobilized on an ITO electrode and characterized by means of XPS, and cyclic voltammetry. The Ru complex monolayers exhibit a reversible Ru(II/III) oxidation at +0.80 V vs. Ag/AgCl in 0.1 M aqueous HClO4. The immobilized Ru complex monolayer is stable over the pH range 1 < pH < 10. The oxidation potential, E1/2, vs. pH plot reveals several lines, indicating that the proton-coupled oxidative reactions occur on the ITO surface. The phosphonate-immobilized Ru dinuclear complex monolayers exhibited a stable electrochromic response on an ITO electrode. The Royal Society of Chemistry 2003. We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 14220-64-5, and how the biochemistry of the body works.Reference of 14220-64-5

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

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Synthesis, structural characterization, photophysical, electrochemical, and anion-sensing studies of luminescent homoand heteroleptic ruthenium(II) and osmium(II) complexes based on terpyridyl-imidazole ligand

A series of hetero- and homoleptic tridentate ruthenium(II) and osmium(II) complexes of compositions [(tpy-PhCH3)Ru(tpy-HImzphen)](ClO 4)2 (1), [(H2pbbzim)-Ru(tpy-HImzphen)](ClO 4)2 (2), and [M(tpy-HImzphen)2]-(ClO 4)2 [M = RuII (3) and OsII (4)], where tpy-PhCH3 = 4?-(4-methylphenyl)-2, 2?:6?, 2?-terpyridine, H2pbbzim = 2, 6-bis-(benzimidazole-2-yl)pyridine and tpy-HImzphen = 2-(4-[2, 2?:6?, 2?]terpyridine-4?-yl- phenyl)-1H-phenanthro[9, 10-d]-imidazole, have been synthesized and characterized by using standard analytical and spectroscopic techniques. X-ray crystal structures of three complexes 2, 3, and 4 have been determined. The absorption spectra, redox behavior, and luminescence properties of the complexes have been thoroughly investigated. All of the complexes display moderately strong luminescence at room temperature with lifetimes in the range of 10-55 ns. The effect of solvents on the absorption and emission spectral behavior of the complexes has also been studied in detail. The anion sensing properties of all the complexes have been studied in solution using absorption, emission, and 1H NMR spectral studies and by cyclic voltammetric (CV) measurements. It has been observed that the complexes 1, 3, and 4 act as sensors for F-only, whereas 2 acts as sensor for F-, AcO-, and to some extent for H2PO4-. It is evident that in the presence of excess of anions deprotonation of the imidazole N-H fragment(s) occurs in all cases, an event which is signaled by the development of vivid colors visible with the naked eye. The receptor-anion binding/equilibrium constants have been evaluated.

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

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A novel 2-D heterometallic polymer containing two types of 1-D cuprous polymeric chains and cir cle [V4O12]4? clusters

A novel 2-D heterometallic polymer [Cu4(biimpy)4(V4O12)]n¡¤2H2O (1, biimpy = 2,6-bis(1-imdazoly)pyridine) has been hydrothermally synthesized and structurally characterized. 1 contains a rare 2-D heterometallic biimply layer built up from the linkages of the circle [V4O12]4? clusters and two types of 1-D cuprous polymeric chains. Although a few cuprous imidazolate derivatives have been reported, their extended structures are generally constructed by only one type of building units. Therefore, 1 provides the rare example of 2-D layer based on two types of building units, namely 1-D cuprous polymeric chains and circle [V4O12]4? clusters. 1 displays selectively photocatalytic of methylene blue under visible light irradiation. Spectroscopic properties and density functional theory calculation of 1 have been also investigated.

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

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Metal thiocyanato complexes: Synthesis, magnetic, and spectral studies of some mixed-ligand thiocyanato complexes of nickel(II) involving benzothiazole and benzimidazole derivatives

A new series of mixed-ligand thiocyanato complexes of nickel(II) of the compositions [Ni(NCS)2(L)4], where L = 2-mercaptobenzothiazole (2-MBZT), 2-(2?-hydroxyphenyl)-benzothiazole (2?-HPBZT), 2-(2?-tolyl)-benzothiazole (2?-TOBZT), 2-(3?-tolyl)benzothiazole (3?-TOBZT), [Ni(NCS)2(2-AMBZT)2] and [Ni(NCS)2(BBZLY)(H2O)2], where 2-AMBZT = 2-aminobenzothiazole and BBZLPY = 2,6-bis(benzimidazole-2?-yl)pyridine, has been synthesized by the interaction of nickel(II) thiocyanate with the respective ligands. The compounds so obtained were characterized by analytical data, molar conductances, magnetic measurements, infrared and electronic spectral studies. Suitable octahedral structures have been suggested for these complexes.

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

Brief introduction of Bis(benzonitrile)palladium chloride

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Synthesis, crystal structure and DNA-binding properties of a nickel(II) complex with 2, 6-bis(2-benzimidazolyl)pyridine

A novel complex of nickel(II) picrate (pic) with the V-shaped ligand 2, 6-bis(2-benzimidazolyl) pyridine (bbp) was synthesized and characterized by elemental analysis, electrical conductivity, and IR and UV/Vis spectral measurements. The crystal structure of the nickel(II) complex ([Ni(bbp) 2](pic)2¡¤2DMF) has been determined by single-crystal X-ray diffraction. The Ni(II) cation is bonded to two bbp ligands through six nitrogen atoms, resulting in a distorted octahedral geometry. The DNA-binding properties of the nickel(II) complex were investigated by electronic absorption and fluorescence spectra and by viscosity measurements. The experimental results suggest that the nickel(II) complex binds to DNA in an intercalation mode.

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

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Ruthenium monoterpyridine complexes with 2,6-bis(benzimidazol-2-yl)pyridine: Synthesis, spectral properties and structure

Ruthenium monoterpyridine complexes with the tridentate 2,6-bis(benzimidazol-2-yl)pyridine (LH2), [Ru(trpy)(LH2)]2+, [1]2+ and [Ru(trpy)(L2-)], 2 (trpy = 2,2?:6?,2?-terpyridine) have been synthesized. The complexes have been authenticated by elemental analyses, UV-Vis, FT-IR, 1H NMR spectra and their single crystal X-ray structures. Complexes [1]2+ and 2 exhibit strong MLCT band near 475 and 509 nm, respectively, and are found to be very much dependent on solution pH. The successive pH dependent dissociations of the N-H protons of benzimidazole moiety of LH2 in [1]2+ lead to the formation of 2. The proton induced inter-convertibility of [1]2+ and 2 has been monitored via UV-Vis spectroscopy and redox features. The two pKa values, 5.75 and 7.70, for complex [1]2+ have been determined spectroscopically.

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

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Synthesis, characterization, self-assembly, gelation, morphology and computational studies of alkynylgold(III) complexes of 2,6-bis(benzimidazol-2′- yl)pyridine derivatives

A novel class of alkynylgold(III) complexes of the dianionic ligands derived from 2,6-bis(benzimidazol-2′-yl)pyridine (H2bzimpy) derivatives has been synthesized and characterized. The structure of one of the complexes has also been determined by X-ray crystallography. Electronic absorption studies showed low-energy absorption bands at 378-466 nm, which are tentatively assigned as metal-perturbed pi-pi* intraligand transitions of the bzimpy2- ligands. A computational study has been performed to provide further insights into the nature of the electronic transitions for this class of complexes. One of the complexes has been found to show gelation properties, driven by pi-pi and hydrophobic-hydrophobic interactions. This complex exhibited concentration- and temperature-dependent 1H NMR spectra. The morphology of the gel has been characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM).

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