Patrick Gamez

Two-Step Relaxation in a Linear Tetranuclear Dysprosium(III) Aggregate Showing Single-Molecule Magnet Behavior

A well-defined two-step relaxation, described by the sum of two modified Debye functions, is observed in a new alkoxido-bridged linear tetranuclear Dy(III) aggregate showing single-molecule magnet behavior with a remarkably large energy barrier. This compound represents a model molecular aggregate with a clear two-step relaxation evidenced by frequency-dependent susceptibility, which therefore may stimulate further investigations regarding the relaxation dynamics of lanthanide-based systems.

Putting Anion–π Interactions Into Perspective

Supramolecular chemistry is a field of scientific exploration that probes the relationship between molecular structure and function. It is the chemistry of the noncovalent bond, which forms the basis of highly specific recognition, transport, and regulation events that actuate biological processes. The classic design principles of supramolecular chemistry include strong, directional interactions like hydrogen bonding, halogen bonding, and cation-π complexation, as well as less directional forces like ion pairing, π-π, solvophobic, and van der Waals potentials. In recent years, the anion-π interaction (an attractive force between an electron-deficient aromatic π system and an anion) has been recognized as a hitherto unexplored noncovalent bond, the nature of which has been interpreted through both experimental and theoretical investigations. The design of selective anion receptors and channels based on this interaction represent important advances in the field of supramolecular chemistry. The objectives of this Review are 1) to discuss current thinking on the nature of this interaction, 2) to survey key experimental work in which anion-π bonding is demonstrated, and 3) to provide insights into the directional nature of anion-π contact in X-ray crystal structures.

Synthetic models of the active site of catechol oxidase: mechanistic studies

The ability of copper proteins to process dioxygen at ambient conditions has inspired numerous research groups to study their structural, spectroscopic and catalytic properties. Catechol oxidase is a type-3 copper enzyme usually encountered in plant tissues and in some insects and crustaceans. It catalyzes the conversion of a large number of catechols into the respective o-benzoquinones, which subsequently auto-polymerize, resulting in the formation of melanin, a dark pigment thought to protect a damaged tissue from pathogens. After the report of the X-ray crystal structure of catechol oxidase a few years earlier, a large number of publications devoted to the biomimetic modeling of its active site appeared in the literature. This critical review (citing 114 references) extensively discusses the synthetic models of this enzyme, with a particular emphasis on the different approaches used in the literature to study the mechanism of the catalytic oxidation of the substrate (catechol) by these compounds. These are the studies on the substrate binding to the model complexes, the structure-activity relationship, the kinetic studies of the catalytic oxidation of the substrate and finally the substrate interaction with (per)oxo-dicopper adducts. The general overview of the recognized types of copper proteins and the detailed description of the crystal structure of catechol oxidase, as well as the proposed mechanisms of the enzymatic cycle are also presented.

Lone pair–π interactions: a new supramolecular bond?

Anion–π interactions have been receiving a great deal of attention from the scientific community for the past five years. This type of non-covalent bond is being recognized as a supramolecular interaction by chemists. Remarkably, the status for the lone pair(lp)-π interaction, namely the bonding association between a neutral electron-rich molecule and an electron-poor π ring, is hardly studied. The importance of lp–π interactions was clearly evidenced in a number of biological systems more than ten years ago; amazingly, only a few examples of lp–π interactions involving small synthetic molecules have been reported so far in the literature. Are these examples unique? Actually, a detailed analysis of the Cambridge Structure Database shows that such interactions are not unusual in organic compounds, but apparently have been overlooked in the past.

Homogeneous bio-inspired copper-catalyzed oxidation reactions

The controlled oxidation of C–H bonds is one of the most challenging and difficult reactions in organic chemistry. Generally, it requires either stoichiometric amounts of toxic heavy metal salts or very expensive catalysts containing transition metals such as palladium, rhodium or ruthenium. The scientific community used to focus their investigations towards these relatively rare and costly elements while neglecting to look at how Nature performs these types of reactions. Biological systems only employ abundantly available metals like iron, zinc and copper. This review summarizes the background and the state of the art of enzymatic and biomimetic oxidation catalysts involving copper as the active metal center. Recent developments have shown the first very promising results in this incipient field.

Iron Spin-Crossover compounds: from fundamental studies to practical applications

Over the past five years, the spin-crossover (SCO) phenomenon has experienced a clear new lease of interest from the scientific community coinciding with the recent publication of remarkable new advances. This perspective paper describes five illustrative examples of SCO systems, published during the past twelve months, showing new aspects of the unique and very appealing behaviour of these molecular switches, which may find interesting applications in the near future.

The Square-Planar Cytotoxic [CuII(pyrimol)Cl] Complex Acts as an Efficient DNA Cleaver without Reductant

Chemical nucleases based on the transition-metal ions cleave DNA hydrolytically and/or oxidatively, with or without added reductant. We report here the novel DNA cleavage properties of the highly water-soluble, square-planar [Cu(Hpyrimol)Cl] complex, together with the results of cytotoxicities toward selected cancer cell lines. The copper complex cleaves PhiX174 supercoiled DNA efficiently without any reductant and shows high cytotoxicities toward L1210 murine leukemia and A2780 human ovarian carcinoma cancer cell lines that are sensitive and resistant to cisplatin. The IC50 values obtained for the copper complex in the sensitive cell lines are in the range of cisplatin, and for the cisplatin-resistant leukemia cell line, this value is even better.

Recent advances in anion–π interactions

Over the past 10 years, anion–π interaction has been recognized as an important weak force that may occur between anionic systems and electron-deficient aromatics. Lately, this supramolecular contact has experienced a rapidly growing interest, as reflected by numerous recent literature reports. The present paper highlights the tremendous progress achieved in the field by emphasizing three important studies involving anion–π interactions published in 2010. In addition, a pioneering search of the Protein Data Bank (PDB) reveals short anion–π contacts in some protein structures.

New polydentate and polynucleating N-donor ligands from amines and 2,4,6-trichloro-1,3,5-triazine

An efficient synthesis of a novel class of multidentate polynucleating ligands has been developed based on high-yielding chloride substitutions of 2,4,6-trichloro-1,3,5-triazine by primary and secondary amines.

Magnetic Properties of Dysprosium Cubanes Dictated by the M−O−M Angles of the [Dy4(μ3-OH)4] Core

Two new dysprosium(III) coordination compounds, namely, [Dy(4)(HL)(4)(C(6)H(4)NH(2)COO)(2)(mu(3)-OH)(4)(mu-OH)(2)(H(2)O)(4)].4CH(3)CN.12H(2)O (1) and Dy(8)(HL)(10)(C(6)H(4)NH(2)COO)(2)(mu(3)-OH)(8)(OH)(2)(NO(3))(2)(H(2)O)(4)] (2), have been synthesized from the Schiff-base ligand 2-{[(2-hydroxy-3-methoxyphenyl)methylidene]amino}benzoic acid (H(2)L) and dysprosium chloride (1) or dysprosium nitrate (2). Single-crystal X-ray diffraction studies reveal that compound 1 exhibits a tetranuclear cubane-like structure and that 2 is an octanuclear, bis-cubane complex. The [Dy(4)(mu (3)-OH)(4)] cubane cores of 1 and 2 are structurally related; however, the magnetic properties of 1 and 2 are drastically different. Indeed, 2 shows slow relaxation of magnetization while no out-of-phase alternating current (ac) signal is noticed for 1. These significant disparities are most likely due to the different M-O-M angles observed for the respective cubane cores.