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Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint?

Molecular magnetism has travelled a long way from the pioneering studies on electron exchange and double exchange or spin crossover and valence tautomerism in small oligonuclear complexes, from mono- to di- and tetranuclear species, to the current investigations about magnetic anisotropy and spin dynamics or quantum coherence of simple mono- or large polynuclear complexes, behaving as switchable bistable molecular nanomagnets for potential applications in information data storage and processing. In this review, we focus on the origin and development of the research in the field of molecular magnetism from a coordination chemistry viewpoint, which dates back to the establishment of magnetochemistry as a novel discipline among the molecular sciences. This overview is conceived as an attempt to orientate coordination chemists regarding their role in the future direction that molecular magnetism will undergo in its further evolution toward molecular spintronics and quantum computation. A particular emphasis will be given to some selected recent advances in single-molecule spintronic circuitry and quantum computing devices based on the large class of multiresponsive and multifunctional magnetic metal complexes to stimulate the progress in the field of molecular magnetism.

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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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Mixed-ligand iridium(III) complexes as photodynamic anticancer agents

Many phosphorescent iridium complexes are potent candidates as photodynamic therapeutic agents. In this work, a series of mixed-ligand phosphorescent iridium complexes (Ir1: [Ir(L1)(bpy)Cl](PF6)2; Ir2: [Ir(L1)(ppy)Cl](PF6); Ir3: [Ir(L2)(bpy)Cl](PF6)2; Ir4: [Ir(L2)(ppy)Cl](PF6). L1 = 2,6-bis(2-benzimidazolyl)pyridine; bpy = 2,2?-bipyridine; L2 = 2,6-bis(1-methyl-benzimidazol-2-yl)pyridine; ppy = 2-phenylpyridine) have been synthesized and characterized. These complexes display high luminescence quantum yields and long phosphorescence lifetimes. All the complexes are resistant to hydrolysis in aqueous solutions, and can produce singlet oxygen (1O2) effectively upon irradiation. Ir1 and Ir2 show pH-sensitive emission properties. Interestingly, higher cellular uptake efficiency is observed for Ir2 and Ir4 with the cyclometalated ppy ligand in human lung adenocarcinoma A549 cells. Ir2 with pH-sensitive emission properties can selectively image lysosomes, and Ir4 can specifically target mitochondria. Both Ir2 and Ir4 exhibit potent photodynamic therapy (PDT) effects, with Ir2 displaying a higher phototoxicity index (PI) especially in A549 cells (PI > 54). Mechanism studies indicate that Ir2 and Ir4 can induce apoptosis through reactive oxygen species (ROS) generation and caspase activation upon visible light (425 nm) irradiation. As expected, Ir2 can damage lysosomes more effectively with a pH-sensitive singlet oxygen (1O2) yield, while Ir4 tends to impair mitochondrial function. Nevertheless, the practical application of Ir2 and Ir4 for PDT may be limited to superficial tumors due to the short excitation wavelength (425 nm). Our study gives insights into the design and anticancer mechanisms of new metal-based PDT anticancer agents.

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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 of Some Imidazole- and Pyrazole- Derived Chelating Agents

Procedures involving condensation of o-phenylenediamines with carboxylic acids, and reaction of bifunctional alkyl halides with bifunctional nucleophiles are described.Syntheses are reported of 2,6-bis(2-benzimidazyl)-pyridine, 1,3-bis(2-benzimidazyl)-2-thiapropane, 1,7-bis(2-benzimidazyl)-2,6-dithiaheptane, 2-hydroxymethyl-5,6-dimethylbenzimidazole, 2-chloromethyl-5,6-dimethylbenzimidazole hydrochloride, 1,7-bis(5,6-dimethyl-2-benzimidazyl)-2,6-dithiaheptane, 3,6-bis(1-pyrazolyl)pyridazine, 2-(2-hydroxy-3-methylphenyl)benzimidazole, 2-(2-hydroxyphenyl)benzimidazole, 5-(2-hydroxyphenyl)-3-methyl-1-phenylpyrazole, 3(5)-(2-hydroxyphenyl)-5(3)-methylpyrazole, 3(5)-(2-hydroxyphenyl)-5(3)-phenylpyrazole, and 1,3-bis((5-methylpyridyl)imino)isoindoline.

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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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2,6-Bis(2-Benzimidazolyl)Pyridine Fluorescent Red-Shifted Sensor for Recognition of Zinc(II) and a Calorimetric Sensor for Iron Ions

The ability of 2,6-bis(2-benzimidazolyl)pyridine (bbp) as an optical sensor was studied by fluorescence spectroscopy, colorimetric and UV-visible techniques. The fluorescence spectra of bbp demonstrated a red-shifted upon addition of Zn2+ ion, whereas rest of the cations did not induce any shift. Selectivity of the sensor was examined toward Zn2+ in the presence of a wide range of cations, as interfering agents, that showed no disruption in its function. In addition, the pH effect was tested on the fluorescence response of bbp; which showed the efficiency of the sensor in a wide pH range. The limit of detection for Zn2+ was estimated as 2.1?muM. Furthermore, the colorimetric studies were carried out and the observations showed a color change from colorless to purple by the addition of Fe2+ ion and from colorless to yellow by the addition of Fe3+. The UV-visible studies were carried out to confirm the colorimetric observations. The color changes occurred when Fe2+ and Fe3+ were added to the sensors solution, respectively. The detection limits were calculated as 2.8?¡Á?10?7?M and 3.5?¡Á?10?6?M for Fe2+ and Fe3+, respectively. Hence, bbp can be used as a dual mode optical sensor for detection of Zn2+ by fluorescence and discriminately detection of Fe2+ and Fe3+ visually.

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

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Cyclometalated Ruthenium(II) Anthraquinone Complexes Exhibit Strong Anticancer Activity in Hypoxic Tumor Cells

Hypoxia is the critical feature of the tumor microenvironment that is known to lead to resistance to many chemotherapeutic drugs. Six novel ruthenium(II) anthraquinone complexes were designed and synthesized; they exhibit similar or superior cytotoxicity compared to cisplatin in hypoxic HeLa, A549, and multidrug-resistant (A549R) tumor cell lines. Their anticancer activities are related to their lipophilicity and cellular uptake; therefore, these physicochemical properties of the complexes can be changed by modifying the ligands to obtain better anticancer candidates. Complex 1, the most potent member of the series, is highly active against hypoxic HeLa cancer cells (IC50=0.53 muM). This complex likely has 46-fold better activity than cisplatin (IC50=24.62 muM) in HeLa cells. This complex tends to accumulate in the mitochondria and the nucleus of hypoxic HeLa cells. Further mechanistic studies show that complex 1 induced cell apoptosis during hypoxia through multiple pathways, including those of DNA damage, mitochondrial dysfunction, and the inhibition of DNA replication and HIF-1alpha expression, making it an outstanding candidate for further in vivo studies. Simply the best: The cytotoxicities of RuII complexes are consistent with their hydrophobicity and cellular uptake properties. Cyclometalated RuII anthraquinone complexes were found to exhibit strong anticancer activity in hypoxic cancer cells through multiple synergistic pathways (see figure).

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

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Anti-HIV and cytotoxic activities of Ru(II)/Ru(III) polypyridyl complexes containing 2,6-(2?-benzimidazolyl)-pyridine/chalcone as co-ligand

Ru(II)/Ru(III) polypyridyl complexes containing 2,6-(2?-benzimidazolyl)-pyridine or chalcone as co-ligands were synthesized and characterized previously (Mishra, L.; Sinha, R. Indian J. Chem., Sec. A 2001, in press. Mishra, L.; Sinha, R. Indian J. Chem., Sec. A, 39A, 2000, 1131). Their interaction with aqueous buffered calf thymus DNA measured. (Novakova, O.; Kasparkova. J.; Vrana, O.; van Vliet, P. M.; Reedijk, J.; Brabec, V., Biochem. 34, 1995, 12369 and these results prompted additional screening for anti-HIV (human immunodeficiency virus) activity against DNA replication in H9 lymphocytes and cytotoxic activity against eight tumor cell lines. The most active compounds were 17 in the former assay (EC50 = 4.1, 3.8, 3.6, and 2.5mug/mL, respectively). Copyright

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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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A metal coordination crosslinking novel high performance thermoset

N-substituted crosslinking polybenzimidazole pyridine sulfone, as novel high performance functional polymers, was prepared 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 were characterized by means of FT-IR and1 H NMR spectroscopy, and the results showed a good agreement with the proposed structures. TGA measurements exhibited that the crosslinking polymers possessed good thermal stability with high thermal decomposition temperatures (thermally stable up to 405-510 C). Additionally, the thermal stability of the coordination polymers was improved constantly with the increasing of the content of Co2+, Ni2+ or Zn2+. The metal coordination crosslinking N-substituted polybenzimidazole pyridine sulfone could be considered as a novel high performance thermoset.

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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, structure, and supramolecular chemistry of three azide manganese complexes with 2, 6-Bis(benzimidazol-2-yl)pyridine

Three azide complexes with the tridentate ligand 2, 6-bis(benzimidazol-2- yl)pyridine (H2BBIP) were synthesized and their complicated supramolecular interactions were investigated with single-crystal X-ray diffraction. Interestingly, the complexes are assembled by bifurcated hydrogen bonding, double helical pi-pi stacking, or anion-pi stacking interactions of the benzimidazole rings by tuning the reaction conditions (temperature, ratio, solvent). Complex 1 is a mononuclear compound, namely, Mn(H 2BBIP)N3(CH3O)¡¤CH3OH. In its 3D supramolecular network, the nitrogen atom of the azide anion is acting as hydrogen bonding bifurcated acceptor. Complex 2 is a dinuclear compound, namely, Mn2(H2BBIP)2(N3) 2¡¤(H2O)0.5. The dinuclear unit is connected by intramolecular pi-pi stacking interactions. Furthermore, double helical pi-pi stacking interactions in the benzimidazole rings are observed. Complex 3, Mn2(H2BBIP)2(N 3)2¡¤CH3OH, can be formulated as a pseudopolymorph of complex 2, which exhibits intramolecular pi-pi stacking interactions as well as anion-pi interactions in the dinuclear unit. Copyright

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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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Spectroscopy and photoredox properties of soluble platinum(II) alkynyl complexes

Six complexes of platinum(II) with a terdentate pi-acceptor ligand, 2,6-(N-(n-hexyl)benzimidazol-2?-yl)pyridine), and different ethynylbenzene ligands were synthesized and investigated by means of optical absorption, luminescence, and time-resolved emission spectroscopy. These complexes display similar photophysical and electrochemical properties as previously investigated analogs with the 2,2?:6?,2?-terpyridine ligand. The energy of the luminescence band maximum is a function of the nature of the chemical substituents attached to the ethynylbenzene ligand, luminescence intensities and lifetimes correlate with the luminescence wavelength according to the energy-gap law. The emissive excited states of some of these complexes are quenched reductively with efficiencies near the diffusion-controlled limit, even for moderate electron donors such as phenothiazine or triphenylamine. A complex with a dimethylamine substituent attached to the ethynylbenzene ligand exhibits photophysical properties that are strongly dependent on the protonation state of the amine. A dimer complex with a diethynyl-substituted xanthene bridging ligand displays absorption and emission behavior that is essentially identical to that of some of the monomeric platinum complexes investigated in this work. Short Pt(II)-Pt(II) contacts are only observed in the crystal structure of a precursor complex. A key feature of the new complexes is their good solubility in common organic solvents, thanks to the presence of two hexyl chains that are attached to the terdentate ligands.

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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, and antimicrobial properties of two cu(II) complexes derived from a benzimidazole ligand

Two copper(II) complexes, [Cu(L)2](ClO4)2] and [Cu(L)(bipy)](ClO4)2, were prepared and characterized by the spectroscopic and analytic methods, where L is N-butylbenzimidazole and bipy is 2,2?-bipyridine. Single crystals of [Cu(L)(bipy)](ClO4)2 suitable for X-ray diffraction study were obtained by slow diffusion of diethyl ether into a DMF solution of the complex and the complex was found to crystallize as [Cu(L)(bipy)](ClO4)2¡¤DMF. The asymmetric unit contains one [Cu(L) (bipy)]2+, two uncoordinated perchlorates, and one DMF solvate. Coordination geometry around Cu (II) is distorted square pyramidal with tau value of 0.31. Thermal properties of the complexes were examined by thermogravimetric analysis, indicating that the complexes are thermally stable to 310C. The metal complexes were screened for their in vitro antibacterial and antifungal activities Bacillus subtilis and Bacillus cereus (as Gram(+) bacteria), Escherichia coli, Enterobacter aerogenes, and Klebsiella pneumoniae (as Gram(?) bacteria), and Saccharomyces cerevisiae, Candida utilis, and Candida albicans (as yeasts). The complexes show antibacterial and antifungal activities against bacteria and yeasts.

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