Clathrochelate Complexes Containing Axial Cymantrene and Tromancenium Moieties

New clathrochelate complexes of manganese, iron and cobalt containing peripheral organometallic manganese moieties cymantrene or tromancenium were synthesized via self-assembly from di/tri-topic dioximes, metal templates and cymantrene/tromancenium boronic acid pinacol esters. These air-stable, highly colored, oligometallic complexes are composed of various combinations of Mn^IFe^IIMn^I, Mn^ICo^IIMn^I, Mn^IMn^IIMn^IIMn^I and Mn^ICo^IICo^IIMn^I metal assemblies with corresponding complicated magnetic and electrochemical properties. Full spectroscopic and structural characterization by ¹H/¹¹B/¹³C NMR, HRMS, IR, UV-vis, single crystal XRD and CV (cyclic voltammetry) is provided. Tetrametallic complexes containing tromanceniumyl substituents with two Co^II or Mn^II central metals exhibit promising anticancer properties against different tumor cell lines.     

Metal–Arene Interactions in Dialkylbiarylphosphane Complexes of Copper,Silver, and Gold

Dialkylbiphenylphosphane–Au^I complexes exhibit only weak metal–arene interactions with the covering arene ring. However, the contacts in isoleptic Ag^I and Cu^I complexes are shorter than the limiting values of 3.03 Å (Ag^I) and 2.83 Å (Cu^I). Strong metal–arene interactions were also found in the two Ag^I aquo complexes and in two acetonitrile? Cu^I complexes with dialkylbiphenylphosphane ligands. Arene–Ag^I complexes with these bulky phosphane ligands show the strongest Ag^I? arene bonds known.     

Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells

Non‐coordinative interactions between a metal ion and the aromatic ring of a fluorophore can act as a versatile sensing mechanism for the detection of metal ions with a large emission change of fluorophores. We report the design of fluorescent probes based on arene–metal‐ion interactions and their biological applications. This study found that various probes having different fluorophores and metal binding units displayed significant emission redshift upon complexation with metal ions, such as Ag^I, Cd^II, Hg^II, and Pb^II. X‐ray crystallography of the complexes confirmed that the metal ions were held in close proximity to the fluorophore to form an arene–metal‐ion interaction. Electronic structure calculations based on TDDFT offered a theoretical basis for the sensing mechanism, thus showing that metal ions electrostatically modulate the energy levels of the molecular orbitals of the fluorophore. A fluorescent probe was successfully applied to the ratiometric detection of the uptake of Cd^II ions and hydrogen sulfide (H₂S) in living cells. These results highlight the utility of interactions between arene groups and metal ions in biological analyses.     

Coordination Chemistry of N‐Heterocyclic Nitrenium‐Based Ligands

Comprehensive studies on the coordination properties of tridentate nitrenium‐based ligands are presented. N‐heterocyclic nitrenium ions demonstrate general and versatile binding abilities to various transition metals, as exemplified by the synthesis and characterization of Rh^I, Rh^III, Mo⁰, Ru⁰, Ru^II, Pd^II, Pt^II, Pt^IV, and Ag^I complexes based on these unusual ligands. Formation of nitrenium–metal bonds is unambiguously confirmed both in solution by selective ¹⁵N‐labeling experiments and in the solid state by X‐ray crystallography. The generality of N‐heterocyclic nitrenium as a ligand is also validated by a systematic DFT study of its affinity towards all second‐row transition and post‐transition metals (Y–Cd) in terms of the corresponding bond‐dissociation energies.     

Sensitized luminescence from lanthanides in d–f bimetallic complexes

This article reviews progress in the research of transition metal–lanthanide (d–f) bimetallic complexes. Through efficient energy transfer, sensitized luminescence of lanthanide ions from the visible range (Eu^III) to the near-infrared region (Nd^III, Yb^III, Er^III and Pr^III) is obtained in these bimetallic assembles. The d-block in d–f bimetallic complexes mainly contributes to the improvement of lanthanide emission efficiency and the extension of the excitation window for the lanthanide complexes. Examples are catalogued by various transition metals, such as Ru^II, Os^II (Fe^II), Pt^II (Au^I), Pd^II, Re^I, Cr^III, Co^III, Zn^II and Ir^III. The relevant synthetic procedures, crystal structures and photophysical properties of these d–f complexes are briefly described. Additionally, the molecular properties responsible for the performance of certain d–f systems, such as energy levels, nuclear distances and coordination environments, will be discussed.     

Reversible M−M Bonding by Alkaline Earth Metals (Mg,Ca, Sr,Ba) in Graphite Intercalation Compounds

The alkaline earth metals (M=Mg, Ca, Sr, and Ba) exhibit a +2 oxidation state in nearly all known stable compounds, but M^I dimeric complexes with M−M bonding, [M₂(en)₂]²⁺, (en=ethylenediamine) of all these metals can be stabilized within the galleries of donor-type graphite intercalation compounds (GICs). These metals can also form GICs with more conventional metal (II) ion complexes, [M(en)₂]²⁺. Here, the facile interconversion between dimeric-M^I and monomeric-M^II intercalates upon the addition/removal of en are reported. Thermogravimetry, powder X-ray diffraction, and pair distribution function analysis of total scattering data support the presence of either [M₂(en)₂]²⁺ or [M(en)₂]²⁺ guests. This phase conversion requires coupling graphene and metal redox centers, with associated reversible M−M bond formation within graphene galleries. This chemistry allows the facile isolation of unusual oxidation states, reveals M⁰→M²⁺ reaction pathways, and present new opportunities in the design of hybrid conversion/intercalation materials for applications such as charge storage.     

Group 9 Metal Complexes of meso‐Aryl‐Substituted Rubyrin

The metalation of meso‐tetrakis(pentafluorophenyl)‐substituted [26]rubyrin has been explored with Group 9 metal salts (Rh^I, Co^II, Ir^III), affording a Hückel aromatic [26]rubyrin–bis‐Rh^I complex with a highly curved gable‐like structure, a Hückel antiaromatic [24]rubyrin–bis‐Co^II complex that displays intramolecular antiferromagnetic coupling between the two Co^II ions (J=?4.5 cm^?1), and two Cp*‐capped Ir^III complexes; in one, the iridium metal sits on the [26]rubyrin frame with two Ir?N bonds, whereas the other has an additional Ir?C bond, although both Ir^III complexes display moderate aromatic character. This work demonstrates characteristic metalation abilities of this [26]rubyrin toward Group 9 metals.     

Electrochemical activity of rhodium complexes supported on fibrous-carbon material

The redox properties of heterogenized Rh^I, Rh^II, and Rh^III complexes with different, particularly organophosphorus, ligands were studied by cyclic voltammetry (CVA). The support is a carbon-paste electrode based on a fibrous-carbon material and activated carbon. The electrochemical reduction of Rh^III produces Rh metal, which further catalyzes hydrogen evolution. After the reduction of water-soluble binuclear Rh^II complexes, the CVA curves exhibit peaks of electrocatalytic hydrogen evolution and irreversible Rh^I→Rh^II oxidation. The Rh^II complexes with organophosphorus ligands are characterized only by the peak of Rh^I→Rh^II oxidation. After reduction, the Rh^I complexes behave as a pseudo-reverse Rh⁰/Rh^I pair. The electron-donating properties of the ligand determine the reversibility of the system. The degree of structurization of the carbon matrix and the presence of phosphorus(v) atoms in it affect the electrochemical activity of the Rh^II and Rh^I complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 908–914, May, 1999.     

Combined EXAFS and DFT Structure Calculations Provide Structural Insights into the 1:1 Multi‐Histidine Complexes of CuII,CuI, and ZnII with the Tandem Octarepeats of the Mammalian Prion Protein

The metal‐coordinating properties of the prion protein (PrP) have been the subject of intense focus and debate since the first reports of its interaction with copper just before the turn of the century. The picture of metal coordination to PrP has been improved and refined over the past decade, but structural details of the various metal coordination modes have not been fully elucidated in some cases. In the present study, we have employed X‐ray absorption near‐edge spectroscopy as well as extended X‐ray absorption fine structure (EXAFS) spectroscopy to structurally characterize the dominant 1:1 coordination modes for Cu^II, Cu^I, and Zn^II with an N‐terminal fragment of PrP. The PrP fragment corresponds to four tandem repeats representative of the mammalian octarepeat domain, designated as OR₄, which is also the most studied PrP fragment for metal interactions, making our findings applicable to a large body of previous work. Density functional theory (DFT) calculations have provided additional structural and thermodynamic data, and candidate structures have been used to inform EXAFS data analysis. The optimized geometries from DFT calculations have been used to identify potential coordination complexes for multi‐histidine coordination of Cu^II, Cu^I, and Zn^II in an aqueous medium, modelled using 4‐methylimidazole to represent the histidine side chain. Through a combination of in silico coordination chemistry as well as rigorous EXAFS curve‐fitting, using full multiple scattering on candidate structures derived from DFT calculations, we have characterized the predominant coordination modes for the 1:1 complexes of Cu^II, Cu^I, and Zn^II with the OR₄ peptide at pH 7.4 at atomic resolution, which are best represented as square‐planar [Cu^II(His)₄]²⁺, digonal [Cu^I(His)₂]⁺, and tetrahedral [Zn^II(His)₃(OH₂)]²⁺, respectively.     

New carbofunctional organosilicon monomers and polymers possessing sorption and metal chromatic properties

Monomeric and polymeric β-naphthylamine and dithizone organosilicon derivatives were synthesized. The organosilicon polymers were studied as sorbents of heavy (Fe^III, Hg^II) and noble (Ag^I, Au^III, Rh^III, Pd^II, Pt^IV) metal ions, as well as of Ce^III and Tb^III. They were found to possess high sorption activity toward platinum group metals and iron. The monomers and polymers obtained exhibit metal chromatic properties. Their reactions virtually with all the elements studied, except cerium and terbium, are accompanied by coloration.     

The Potential of π-Bonded Organometallic Polymers in Catalyst Design

Reductive substitution, the process whereby a hydrocarbon ligand, usually a cyclopentadienyl group, in a transition metal complex is replaced by another unsaturated hydrocarbon with concomitant metal reduction has been utilized to prepare novel complexes of Cr°, Cr^I, Mn^I, Co^I and Ni°. Similarly, ligand substitution, defined more generally as replacement of ligand(s) of a metal complex by an unsaturated hydrocarbon but with no change in the oxidation state of the metal, has resulted in the synthesis of a series of tetraphenylborate and substituted tetraphenylborate complexes of Fe^II, Mo^I, Cr^I, W^I, and Co^I. These procedures and the complexes derived therefrom are considered models for polymers incorporating a variety of novel features.     

Photochromic bipyridyl metal complexes: Photoregulation of the nonlinear optical and/or luminescent properties

The combination of transition metals and ligands featuring photochromic units is receiving much attention and opens up new perspectives for the design of metal-based photoswitchable molecules. This account summarizes some of our recent works made in the area of photochromic organometallic and coordination compounds, which have been used for the photomodulation of the quadratic non-linear optical (NLO) properties, as well as of the photoregulation of the emission properties of the resulting systems. For this purpose, we have designed new chromophores combining dithienylethene (DTE)-based bipyridine ligands with different metallic fragments (Re^I, Fe^II, Ru^II, Ir^III, Cu^I, Zn^II), giving rise to multi-photochromic metal complexes containing from two to six DTE units, and studied the photocontrol of both NLO and luminescence properties.     

Chromium(0), Molybdenum(0), and Tungsten(0) Isocyanide Complexes as Luminophores and Photosensitizers with Long-Lived Excited States

Arylisocyanide complexes based on earth-abundant Group 6 d⁶ metals are interesting alternatives to photoactive complexes made from precious metals such as Ru^II, Re^I, Os^II, or Ir^III. Some of these complexes have long-lived ³MLCT excited states that exhibit luminescence with good quantum yields as well as nano- to microsecond lifetimes, and they are very strongly reducing. Recent studies have demonstrated that Cr⁰, Mo⁰, and W⁰ arylisocyanide complexes have great potential for applications in luminescent devices, photoredox catalysis, and dye-sensitized solar cells.     

Beiträge zur Komplexchemie der Phosphine und Phosphinoxide. XXIII. Schwermetallkomplexe des Tetramethyl-biphosphins

On the coordination chemistry of phosphines and phosphinoxides. XXIII. Heavy metal complexes of tetramethyl-biphosphine The reactions of tetramethyl-biphosphine with salts of 3d elements including Cd and Hg, too, in THF, benzene, acetonitrile and alcohols, respectively, results in forming complexes of differing compositions: (MⁿX_n)₂{(CH₃)₂P? P(CH₃}₂)₃? Mⁿ = Ti^III, V^III, Cr^III, Fe^II, Ni^II, Cu^I; MX₂{(CH₃)₂P? P(CH₃)₂}₂? M = Co^II, Ni^II, Hg^II; MX₂ · (CH₃)₂P? P(CH₃)₂? M = Fe^II, Ni^II, Zn, Cd, Hg^II; X = Cl, Br, J. The partly intensively coloured complexes have low solubilities; this item complicates the performing of structure determining methods. Partial informations about the structures of the complexes are to be gained by magnetic and spectrophotometric measurements and X-ray investigations. The tendency of (CH₃)₂P? P(CH₃)₂ to form complexes with transition metals differs from that of other biphosphines. Splitting of the P? P bond due to metal salts does not occur. (CH₃)₂P? P(CH₃)₂ acts as a monodentate or bidentate ligand, like other members of the R₂P? PR₂ series do too. The forming of ligand bridges seems to be favoured in comparison to the chelate function.     

The synthesis,spectroscopic and thermal study of oxamic acid compounds of some metal(II) ions

Summary The preparation of oxamic acid complexes of general formula M(H₂NCOCOO)₂·xH₂O (M = Mn^II, Co^II, Ni^II, Cu^II or Zn^II; x = 1 for Cu^II, x = 2 for the other metals) is reported. The i.r. and Raman spectra are discussed considering a trans-octahedral structure, formed by five-membered chelate rings with the amide oxygen and one carboxylic oxygen as donor atoms. The apical positions are occupied by water molecules. The thermal degradation process is very similar for the different complexes, first losing H₂O in one or different steps, then the fragments of the organic ligand to give the metal oxide as residue. The thermal degradation of the Cu^II and Zn^II compounds results in the formation of a new polymeric compound by deprotonation of the primary amide function in an endothermic process, the polymer further decomposes to form the metal oxide.     

New organosilicon derivatives of some analytical reagents: sorbents and metallochromic agents

A synthesis of organosilicon monomeric and polymeric derivatives of 1,4-phenylenediamine, 4-aminoantipyrine, and aniline, which are analytical agents possessing sorption properties, was accomplished. The synthesized organosilicon polymers were studied as sorbents of heavy metals Fe^III, Hg^II and noble metals Ag^I, Au^III, Rh^III, Pd^II, Pt^IV. Poly[(3-N-silsesquioxanylpropyl-4aminoantipyrine)] exhibited high sorption activity with respect to platinum group metals in comparison with poly[N,N´-bis(3-silsesquioxanylpropyl)-1,4-phenylenediamine]. The reaction of poly[(3-N-silsesquioxanylpropyl-4-aminoantipyrine)] practically with all the elements under study was accompanied by coloring. The starting monomer exhibited similar metallochromic properties.     

The Charge Transfer Approach to Heavier Main‐Group Element Radicals in Transition‐Metal Complexes

The Co^II and Fe^II complexes 1Co and 1Fe with a coordinated phosphorus radical were easily obtained through a charge‐transfer approach from the M^I precursors LM^I(tol) (M=Co, Fe; L=CH(MeC=NDipp)₂, Dipp=2,6‐i Pr₂C₆H₃) to the diazafluorenylidene‐substituted phosphaalkene 1 . Structural, magnetic, and computational studies on 1Co and 1Fe indicate a weak antiferromagnetic interaction between the high‐spin M^II ion and the phosphorus radical, resulting in a triplet and quartet ground state, respectively. Complexes 1Co and 1Fe are the first examples of phosphorus‐radical‐coordinated transition‐metal complexes synthesized by charge transfer, providing a new approach to access radicals of heavier main‐group elements.     

Synthesis,characterization and antimicrobial studies on 13-membered-N6-macrocyclic transition metal complexes containing trimethoprim

Asymmetrical macrocyclic complexes of Mn^II, Co^II, Ni^II, Cu^II and Zn^II have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X₂] (M = Mn^II, Co^II, Ni^II, Cu^II and Zn^II, L = ligand and X = Cl^?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X₂] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X₂] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X₂] complexes exhibit potent broad spectrum antibacterial activity.     

Synthesis,structure, and fungicidal activity of mono- and binuclear mixed-ligand copper complex with <Emphasis Type="Italic">p</Emphasis>-nitrobenzoic acid and monoethanolamine

Mixed-ligand metal complexes based on ethanolamines and simple monosubstituted benzoic acids, in particular, mono- and binuclear copper complexes with monoethanolamine (MEA) and p-nitrobenzoic acid (PNBA), [Cu²⁺((PNBA)₂ ^-(MEA)₂)] (I) and [2Cu²⁺((PNBA)₄ ^-(MEA)₂(H₂O)₂)] (II), were prepared for the first time. The structures of the complexes were characterized by FT IR spectroscopy and X-ray diffraction (CIF files CCDC no. 1497849 (I) and no. 1497848 (II)). The doubly charged copper ions are coordinated at the vertices of octahedra, which are highly distorted due to the Jahn–Teller effect. In the crystals of the mononuclear complex I, the molecules are joined into columns, whereas in the binuclear compound II, a three-dimensional framework is formed owing to intermolecular H-bonds involving the nitro group. Fungicidal activities were found for compounds I, II, MEA, PNBA, previously obtained single-ligand copper complexes with MEA and PNBA, and MEA- and PNBA-based organic salt. The biological activity gradually increases in the series: ligand, single-ligand metal complex, organic salt, mono- and binuclear mixed-ligand complex, i.e., some ligands and copper ions show a synergistic effect.     

Synthesis,Spectral, Thermal Studies of Co(II), Ni(II), Cu(II) and Zn(II)‐arginato Complexes. Crystal Structure of Monoaquabis(arginato‐κO,κN)copper(II). [Cu(arg)2(H2O)].NaNO3

Transition metal complexes of arginine (using Co(II), Ni(II), Cu(II) and Zn(II) cations separately) were synthesized and characterized by FTIR, TG/DTA‐DrTG, UV‐Vis spectroscopy and elemental analysis methods. Cu(II)‐Arg complex crystals was found suitable for x‐ray diffraction studies. It was contained, one mole Cu^II and Na⁺ ions, two arginate ligands, one coordinated aqua ligand and one solvent NO₃^? group in the asymmetric unit. The principle coordination sites of metal atom have been occupied by two N atoms of arginate ligands, two carboxylate O atoms, while the apical site was occupied by one O atom for Cu^II cation and two O atoms for Co^II, Ni^II, Zn^II atoms of aqua ligands. Although Cu^II ion adopts a square pyramidal geometry of the structure. Co^II, Ni^II, Zn^II cations have octahedral due to coordination number of these metals. Neighbouring chains were linked together to form a three‐dimensional network via hydrogen‐bonding between coordinated water molecule, amino atoms and O atoms of the bridging carboxylate groups. Cu^II complex was crystallized in the monoclinic space group P2₁, a = 8.4407(5) Å, b = 12.0976(5) Å, c = 10.2448(6) Å, V = 1041.03(10) ų, Z = 2. Structures of the other metal complexes were similar to CuII complex, because of their spectroscopic studies have in agreement with each other. Copper complex has shown DNA like helix chain structure. Lastly, anti‐bacterial, anti‐microbial and anti‐fungal biological activities of complexes were investigated.