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A new mononuclear rhodium(III) complex, [Rh(bzimpy)Cl3] (bzimpy = 2,6-bis(2-benzimidazolyl)pyridine), was synthesized and characterized by elemental analysis and spectroscopic methods. The molecular structure of the complex was confirmed by single-crystal X-ray crystallography. The interaction of the complex with fish sperm DNA (FS-DNA) was investigated by UV spectroscopy, emission titration, and viscosity measurement in order to evaluate the possible DNA-binding mode and to calculate the corresponding DNA-binding constant. The results reveal that the Rh(III) complex interacts with DNA through groove binding mode with a binding affinity on the order of 104. In addition, the binding of the Rh(III) complex to bovine serum albumin (BSA) was monitored by UV?Vis and fluorescence emission spectroscopy at different temperatures. The mechanism of the complex interaction was found to be static quenching. The thermodynamic parameters (DeltaH, DeltaS, and DeltaG) obtained from the fluorescence spectroscopy data show that van der Waals interactions and hydrogen bonds play a major role in the binding of the Rh(III) complex to BSA. For the comparison of the DNA- and BSA-binding affinities of the free bzimpy ligand with its Rh(III) complex, the absorbance titration and fluorescence quenching experiments of the free bzimpy ligand with DNA and BSA were carried out. Competitive experiments using eosin Y and ibuprofen as site markers indicated that the complex was mainly located in the hydrophobic cavity of site I of the protein. These experimental results were confirmed by the results of molecular docking. Finally, the in vitro cytotoxicity properties of the Rh(III) complex against the MCF-7, K562, and HT-29 cell lines were evaluated and compared with those of the free ligand (bzimpy). It was found that the complexation process improved the anticancer activity significantly.

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

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Intrigued by the unexpected room-temperature dual visible/near-infrared (NIR) luminescence observed for fast-relaxing erbium complexes embedded in triple-stranded helicates, in this contribution, we explore a series of six tridentate N-donor receptors L4?L9 with variable aromaticities and alkyl substituents to extricate the stereoelectronic features responsible for such scarce optical signatures. Detailed solid-state (X-ray diffraction, differential scanning calorimetry, optical spectroscopy) and solution (speciations and thermodynamic stabilities, spectrophotometry, NMR and optical spectroscopy) studies of mononuclear unsaturated [Er(Lk)2]3+ and saturated triple-helical [Er(Lk)3]3+ model complexes reveal that the stereoelectronic changes induced by the organic ligands affect inter- and intramolecular interactions to such an extent that 1) melting temperatures in solids, 2) the affinity for trivalent erbium in solution, and 3) optical properties in luminescent complexes can be rationally varied and controlled. With this toolkit in hand, mononuclear erbium complexes with low stabilities displaying only NIR emission can be transformed into molecular-based dual Er-centered visible/NIR emitters operating at room temperature in both solid and solution states.

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

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[Pb2(boa)(Hbbp)2] has been synthesized by treating 4-carboxylphenoxyacetic (H2boa) and 2,6-bis(benzimidazolyl)pyridine (H2bbp) with metal salts under hydrothermal conditions. Adjacent metal centers forms dinuclear metal complex through carboxylato groups as building blocks. The arrangement of the half deprotonated H2bbp ligand and carboxylate groups exhibits a coordination gap around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on Pb(II), with the coordination environment around the lead atoms is hemidirected. This system is a particularly clear example that coordination sphere of a unique dinuclear Pb(II) compound was controlled by lone pair activity, weak Pb???O interactions, pi-pi stacking and the hydrogen bonds. The above weak interactions influence differently strong red-shifted effect about the solution and solid-state photoluminescence of the compound, compared to the free ligand.

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

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Reported herein is the first example of the Rh(NHC)-catalyzed selective bis C-H alkylation of NNN tridentate chelating compounds in reaction with alkenes. The observed excellent site-selectivity can readily be explained by the postulated rollover pathway in the C-H bond activation step. The reaction is highly facile affording bis-alkylated tridentate products in high yields over a broad range of versatile heteroarene substrates and alkene reactants including ethylene gas, thus enabling its applications to be feasible in coordination and synthetic 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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Herein, we discuss how, why, and when cascade complexation reactions produce stable, mononuclear, luminescent ternary complexes, by considering the binding of hexafluoroacetylacetonate anions (hfac-) and neutral, semi-rigid, tridentate 2,6-bis(benzimidazol-2-yl)pyridine ligands (Lk) to trivalent lanthanide atoms (LnIII). The solid-state structures of [Ln(Lk)(hfac)3] (Ln=La, Eu, Lu) showed that [Ln(hfac)3] behaved as a neutral six-coordinate lanthanide carrier with remarkable properties: 1)the strong cohesion between the trivalent cation and the didentate hfac anions prevented salt dissociation; 2)the electron-withdrawing trifluoromethyl substituents limited charge-neutralization and favored cascade complexation with Lk; 3)-nine-coordination was preserved for [Ln(Lk)(hfac) 3] for the complete lanthanide series, whilst a counterintuitive trend showed that the complexes formed with the smaller lanthanide elements were destabilized. Thermodynamic and NMR spectroscopic studies in solution confirmed that these characteristics were retained for solvated molecules, but the operation of concerted anion/ligand transfers with the larger cations induced subtle structural variations. Combined with the strong red photoluminescence of [Eu(Lk)(hfac)3], the ternary system LnIII/hfac -/Lk is a promising candidate for the planned metal-loading of preformed multi-tridentate polymers.

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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 synthesized three types of binuclear Ru complexes (1-3) that contain pyrene anchors for the adsorption of 1-3 onto nanocarbon materials via noncovalent pi-pi interactions, in order to investigate their adsorption onto and their desorption from highly ordered pyrolytic graphite (HOPG). The adsorption saturation for 1 (6.22 pmol/cm2), 2 (2.83 pmol/cm2), and 3 (3.53 pmol/cm2) on HOPG was obtained from Langmuir isotherms. The desorption rate from HOPG electrodes decreased in the order 3 (2.4 ¡Á 10-5 s-1) > 2 (1.4 ¡Á 10-5 s-1) ? 1 (1.8 ¡Á 10-6 s-1). These results indicate that the number of pyrene anchors and their position of substitution in such complexes strongly affect the desorption behavior. However, neither the free energy of adsorption (DeltaGads) nor the heterogeneous electron-transfer rate (kET) showed any significant differences among 1-3, albeit that the surface morphologies of the modified HOPG substrates showed domain structures that were characteristic for each Ru complex. In the case of 3, the average height changed from ?2 to ?4 nm upon increasing the concentration of the solution of 3 that was used for the surface modification. In contrast, the height for 1 and 2 remained constant (1.5-2 nm) upon increasing the concentration of the complexes in the corresponding solutions. While the molecular orientation of the Ru-Ru axis of 3 relative to the HOPG surface normal changed from parallel to perpendicular, the Ru-Ru axis in 1 and 2 remained parallel, which leads to an increased stability of 1 and 2.

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

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Stereospecific polymerizations of 1,3-butadiene catalyzed by Co(II) complexes ligated by 2,6-bis(benzimidazolyl)pyridines

Highly stereoregular polybutadiene polymers with 1,4-cis isomeric content is synthesized using a series of 2,6-bis(benzimidazolyl)pyridine Co(II) on activation with alkylaluminum cocatalysts under moderate reaction conditions.

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

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New Iron(II) Spin-crossover Complexes with Heterocyclic Amine-derived Ligands and STEPS Experiments on Photogenerated Metastable High-spin States

Cationic complexes of the type 2+ and 2+ have been isolated as Cl-, ClO4-, or BF4- salts, where LNN and LNNN represent bidentate and tridentate nitrogen-donor ligands respectively.The bidentate ligands were 2-(2’pyridyl)benzimidazole (pybzim), 2-(2′-pyridyl)-N-methylbenzimidazole (mpybzim); 2-(2′-pyridyl)benzothiazole (pybzt), 2,2′-dipyridylamine (dpya), and the tridentates di(2-pyridylmethyl)amine (dpyma), 2,6-bis(benzimidazol-2′-yl)pyridine (bzimpy), 2,6-bis(N-methylbenzimidazol-2′-yl)pyridine (mbzimpy), and 2,6-bis(benzothiazol-2′-yl)pyridine (bztpy).Except for , all these FeN6 chromophores exhibit strong absorption in the 550 nm region, which is assigned as a metal-to-ligand charge-transfer transition.Between 4 and 320 K, the iron(II) is in the low-spin form in the majority of these compounds; high-spin exceptions are 2 and Cl2.Other complexes show evidence of the onset of a spin transition near 40 deg C, while the salt *CHCl3 is a well defined spin-crossover system.The low-spin complex 2 was excited by irradiation with visible light, and the generation and decay of resulting high-spin form was observed under cryogenic conditions.In solution, 2+ acts as a weak diprotic acid and also exhibits quintet ->/<- singlet spin crossover (DeltaHo = -42.7 kJmol-1, DeltaSo = -140.9 JK-1mol-1).The complexes are all electrochemically oxidizable to their iron(III) forms in non-aqueous solution, but the dpyma, bztpy, pybtz, and dpya chelates thus formed are unstable.The iron(III) complex – containing the doubly deprotonated ligand was obtained as its low-spin triethylammonium salt.The high-spin chloro complexes . , Fe(mbzimpy)Cl2, and the mixed-spin iron(II) complex salt were also isolated.

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

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Synthesis, electrochemical, and molecular inclusion properties of ‘canopied’ trinuclear ruthenium complexes with six anchoring groups on an ITO electrode

New trinuclear Ru complexes bearing both 1,3,5-tris(2,2?:6?, 2?-terpyridyl)benzene and bis(benzimidazol-2-yl)pyridine with six phosphonate anchors were synthesised and immobilised on an ITO electrode. The ‘canopied’ structure was proved by AFM measurements. The immobilised Ru trinuclear complex revealed a one step three-electron oxidation process for the Ru(II/III) couple at around +0.9 V vs. Ag/AgCl, indicating that the Ru-Ru interaction is small. For the Ru immobilised ITO surface, the electron transfer blocking and the electron mediation of [Fe(CN)6]4- oxidation through the Ru(iii)Ru(ii) catalytic cycle are strongly dependent on the alkyl chain length. The spectroelectrochemistry of the Ru trinuclear complex monolayer on the ITO electrode showed a stable electrochromic response under the potential pulse. The present ‘canopied’ Ru trinuclear complexes hold a small cavity that encapsulates tetrathiafulvalene molecules, which can be proved by a cyclic voltammogram.

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

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Synthesis and dynamic NMR studies of rhenium(I) tricarbonyl bromide complexes of benzimidazolylpyridine ligands. Crystal structure of [ReBr(CO)3{2,6-bis(1?, 5?, 6?-trimethylbenzimidazol-2?-yl)pyridine}]

Pentacarbonylbromorhenium(I) reacted with 2,6-bis(benzimidazol-2?-yl)pyridine (bbip), 2,6-bis(1?-methylbenzimidazol-2?-yl)pyridine (bmbip), 2,6-bis(5?,6?-dimethylbenzimidazol-2?-yl)pyridine (bdmbip), and 2,6-bis(1?,5?,6?-trimethylbenzimidazol-2?-yl)pyridine (btmbip) to form stable octahedral complexes of type fac-[ReBr(CO)3L] (L=bbip, bmbip, bdmbip or btmbip) in which L is acting as a bidentate chelate ligand. At above-ambient temperatures in solution the complexes are fluxional with the nitrogen ligand oscillating between equivalent bidentate bonding modes. Rates and activation energies for these fluxions have been investigated by NMR methods. At low temperatures rotation of the uncoordinated benzimidazolyl unit is restricted and for fac-[ReBr(CO)3(btmbip)] in CD2Cl2 solution, two preferred rotamers exist in 89:11% relative abundances. A rotational energy barrier has been estimated. The X-ray crystal structure of fac-[ReBr(CO)3)(btmbip)] confirms the bidentate chelate bonding of btmbip with a N-Re-N angle of 74.2. The pendant benzimidazole unit is inclined at an angle of 60.7 to the pyridine ring.

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