Di- and Trinuclear σ-Aryl Iron and Manganese Complexes

Reactions of p- and m-diiodobenzenes, p,p'-diiodobiphenyl, and 1,3,5-triiodobenzene with anions derived from dicarbonyl(cyclopentadienyl)iron and pentacarbonylmanganese, catalyzed by palladium complexes, provide a successful route to mono-, di-, and trinuclear -aryl iron and manganese complexes.     

Investigation on Magnetic Properties of Exchange Coupled Transition Metal Complexes Ⅱ．Theoretical Model for Trinuclear Complexes

ＩｎｖｅｓｔｉｇａｔｉｏｎｏｎＭａｇｎｅｔｉｃＰｒｏｐｅｒｔｉｅｓｏｆＥｘｃｈａｎｇｅＣｏｕｐｌｅｄＴｒａｎｓｉｔｉｏｎＭｅｔａｌＣｏｍｐｌｅｘｅｓⅡ．ＴｈｅｏｒｅｔｉｃａｌＭｏｄｅｌｆｏｒＴｒｉｎｕｃｌｅａｒＣｏｍｐｌｅｘｅｓＸｉｅＸｉｕ－Ｌａｎ；...     

Syntheses and Magnetism of μ-1, 3, 5-Benzenetricarboxylato Trinuclear Manganese(Ⅱ) and Nickel(Ⅱ)Complexes

IntroductionThestudyofmagneticexchangeinteractionbetweenparamagneticcenterspropagatedbymulti-atombridgesisofcurrentinterestduetounderstandingthepathwayofelectrontransferinbio1ogicalsystemandobtainingsomeusefulin-formationaboutdesigningmolecule-basedmagnets.Manypapers['-'Jdealingwithphthalato,isophthalatoandterephthalatoligandsasamulti-atombridgeshavebeenpublished.1thasbeenrevealedbythevariable-temperaturemagneticsusceptibilityinvestigationthatlong-rangemagneticcouplingoccursbetweentwoparamagne…     

Trinuclear Organometallic Pt−Ir−Pt Complexes: Insights into Photophysical Properties,Amino Acid Binding and Protein Sensing

The rational synthesis of trinuclear emissive organometallic complexes with two equivalent platinum(II) centres appended to the ancillary substituted 2,2′-bipyridyl ligand of the cyclometalated iridium(III) centre is reported here. The alkynyl-platinum moiety and cyclometalated iridium(III) centres have been separated through a non-conjugated CH₂−O−CH₂ linkage. The emission titration with amino acids reveals that the complexes sense free amino acids. The luminescence sensing of BSA is thus attributed to the amino acid sensing ability of the complexes and confirmed by emission anisotropy and Far-UV CD spectral study. The decrease in α-helix in the CD spectra signifies the changes in the secondary structure of protein in presence of the complexes.     

DNA Binding Properties and Cytotoxic Activities of Two Trinuclear Ruthenium（Ⅱ） Polypyridyl Complexes

The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as viscosity measurement. The results indicate that complexes 1 and 2 bind to DNA via the interaction of the planar π-delocalized system of the complexes with intrinsic binding constants of 4.18 × 10^5 and 3.85 × 10^6 L/tool, respectively, and non-electrostatic binding free energy makes a predominant contribution to the binding free energy. The in vitro cytotoxic activity of complexes 1 and 2 was evaluated by the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl- 2H-tetrazolium bromide] method. Complex I shows higher anticancer potency than complex 2 against four tumor cell lines. Further mechanism study indicates that complexes 1 and 2 can cause cell cycle arrest in the G2/M phase.     

Crystal Structures and Magnetic Properties of Cu(II) Complexes with Pyrazole‐Substituted Iminonitroxyl Radicals: New Trinuclear Heterospin Complexes

The paper describes the crystal structures and magnetic properties of complexes of copper(II) hexafluoroacetate (Cu(hfac)₂) with stable pyrazolesubstituted iminonitroxyl radicals containing the pyrazole substitutuent in the second position of the 2imidazoline cycle (L). A new group of [Cu(hfac)₂]₃(L)₂ complexes is found, in which L performs a bidentatebridge function due to the coordination of the imine N atoms of the pyrazole and imidazoline cycles. It is shown that in the solid complexes there are Cu²⁺—N = C—N—O exchange routes with highenergy ferromagnetic interactions (60–100 cm^-1).     

Synthesis, Characterization and Luminescence Studies of Trinuclear Rhenium–Cobalt Mixed-Metal Alkynyl Complexes Containing a Tetrahedral Co2C2 Cluster Unit

The reaction of rhenium(I) diynyl complexes [Re(CO)₃(N–N)(CC--CCH)] [N–N = ^tBu₂bpy (1), bpy (2)] with Co₂(CO)₈ in THF yielded a new class of luminescent trinuclear rhenium–cobalt mixed-metal alkynyl complexes, [Co₂{-HC₂CC[Re(CO)₃(N–N)]}(CO)₆] [N–N = ^tBu₂bpy (3), bpy (4)]. Their luminescence and electrochemical properties have also been studied.     

Trinuclear and Dinuclear Manganese Complexes of 2/4-Formylbenzoic Acid Oxime Ligands： Syntheses and Crystal Structures

Two manganese complexes, [Mn3（2-cba）6（phen）2] 1 （2-cba = 2-cyanobenzoic acid, phe11 = 1,10-phenanthroline） and [MnE（4-fbaO）E（phen）4]（PF6）E.EHEO 2 （4-fbao = 4-formylbenzoic acid oxime）, have been synthesized by the reaction of 2-formylbenzoic acid oxime （2-fbao, HELl） or 4-formylbenzoic acid oxime （4-fbao, HELE） with phen and manganese acetate in ethanol or methanol solution. A translation from the oximino （-CHN=OH） of HELl to cyano （-C-N） was found in the formation of complex 1 at room temperature. The complexes were structurally determined by single-crystal X-ray diffraction. The crystal of compound I belongs to monoclinic, space group C2/c, with a = 17.983（6）, b = 23.364（7）, c =14.589（5） A, β = 92.401（5）° V = 6124（3） A^3, Z = 4, C72H40Mn3N10O12, Mr= 1401.96, Dc = 1.521 g/cm^3, F（000） = 2852.0, Rint = 0.0372, T= 293（2） K,μ = 0.686 mm^-1, the final R = 0.0644 and wR = 0.1813 for 5803 observed reflections with I 〉 2δ（I）. The crystal of compound 2 is of monoclinic system, space group P21/n, with a = 13.050（4）, b = 20.577（5）, c = 13.323（4）A,β = 113.578（3）°, V = 3227.2（14）A3, Z = 2, C64H48F12Mn2N10O8P2, Mr = 1484.94, Dc = 1.528 g/cm^3, F（000） = 1508.0, Rint= 0.0295, T= 293（2） K,μ = 0.539 mm^-1, the final R = 0.0629 and wR = 0.1789 for 5298 observed reflections with I 〉 2σ（I）. Compounds 1 and 2 are linear trinuclear and dinuclear manganese complexes respectively, which are both bridged by carboxylate groups of the ligands.     

Influence of Changing the Remote Substituents on Charge Transfer Properties of Cyanide-Bridged Trinuclear Fe−Ru−Fe Complexes

To investigate the effect of ligand remote (>10 Å) substituents on the bridging metal center on the metal-to-metal charge transfer (MMCT) properties in cyanidometa-bridged complexes, a series of new cyanidometal-bridged complexes and their one-electron and two-electron oxidation products have been synthesized and well characterized (namely, trans-[Cp(dppe)Fe−NC−(L)Ru(PPh₃)−CN−Fe(dppe)Cp][PF₆]_n (n=2, 3, 4) (L=dmptpy, 1[PF₆]_n ; L=meoptpy, 2[PF₆]_n ; L=t-Buptpy, 3[PF₆]_n ) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, PPh₃=triphenylphosphine, dmptpy=4′-(4-dimethylaminophenyl)-2,2′,6′,2′′-terpyridine, meoptpy=4′-(4-methoxyphenyl)-2,2′,6′,2′′-terpyridine, t-Buptpy=4′-(4-tertbutylphenyl)-2,2′,6′,2′′-terpyridine)). The investigations suggest that the cyanido-stretching (ν_CN) vibration energy for the complexes is unsensitive to the electron-donating ability change of the remote substituents of the cyanidometal bridging auxiliary ligand from tertbutyl, methoxy to dimethylamino group. However, the MMCT energies of the one- and two-electron oxidation complexes are still sensitive to the remote substituents of the ligand on the bridging metal center, and decreases with the increase of the electron-donating ability of the remote substituents from tertbutyl, methoxy to dimethylamino group. All one-electron and two-electron oxidation products belong to Class II mixed valence compounds according to the classification of Robin and Day.     

The Electronic Structures and Chemical Bonding of Some Dinuclear and Trinuclear Low－valence Molybdenum Complexes Containing Thiolate Bridges

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Synthesis,Structure and Reactivity of Lanthanocene Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｃｈｅｍｉｓｔｒｙｏｆｏｒｇａｎｏｌａｎｔｈａｎｉｄｅｓｈａｓｅｘｐｅｒｉｅｎｃｅｄｅｘｔｒｅｍｅｌｙｉｍｐｏｒｔａｎｔｄｅｖｅｌｏｐｍｅｎｔｓｄｕｒｉｎｇｔｈｅｌａｓｔｔｗｏｄｅｃａｄｅｓ ,ａｎｄｎｕｍｅｒｏｕｓｕｎｕｓｕａｌｃｏｍｐｏｕｎｄｓｗｉｔｈｕｎｐｒｅｃｅ ｄｅｎｔｅｄｓｔｒｕｃｔｕｒｅｓａｎｄｕｎｉｑｕｅｒｅａｃｔｉｖｉｔｙｐａｔｔｅｒｎｓｈａｖｅｂｅｅｎｐｒｅｐａｒｅｄ .1ＯｒｇａｎｏｌａｎｔｈａｎｉｄｅｃｏｍｐｏｕｎｄｓｃｏｎｔａｉｎｉｎｇＬｎ—Ｃ ,…     

A Novel Biferrocene Trinuclear Complex with Cis-Configuration

Recently,organometallicmaterialshavebeenattractingagreatdealofattentioninthefieldofnonlinearoptics"'.Sandwich-typecompounds,likeferrocene,areexamplesoforganometallicsystemsofpotentialinterestbecausetheycontainaromaticcyclopentadienylringsinteractingw...     

CrystalStructure and Third-orderNonlinear OpticalProperties ofcis-ConfigurationBiferrocene Trinuclear Com plexes

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｃｅｎｔｌｙ，ｏｒｇａｎｏｍｅｔａｌｌｉｃｍａｔｅｒｉａｌｓｈａｖｅｂｅｅｎａｔｔｒａｃｔｉｎｇｍｕｃｈａｔｔｅｎｔｉｏｎｉｎｔｈｅｆｉｅｌｄｏｆｎｏｎｌｉｎｅａｒｏｐｔｉｃｓ［１，２］．Ｌｉｋｅｏｒｇａｎｉｃｍａｔｅｒｉａｌｓ，ｏｒｇａｎｏｍｅｔａｌｌｉｃｃｏｍｐｏｕｎｄｓａｌｓｏｏｆｆｅｒｔｈｅａｄｖａｎｔａｇｅｓｏｆａｒｃｈｉｔｅｃｔｕｒａｌｆｌｅｘｉｂｉｌｉｔｙ，ｅａｓｅｏｆｆａｂｒｉｃａｔｉｏｎａｎｄｔａｉｌｏｒｉｎｇ．Ａｎｉｍｐｏｒｔａｎｔａｓｐｅｃｔｏｆ…     

Trinuclear zinc β-naphthoate complexes: synthesis and structure

New trinuclear Zn^II β-naphthoate complexes with mono- and bidentate N-donor ligands (2,3-lutidine (lut), 1,10-phenanthroline (phen), and 5,5′-di-tert-butyl-2,2′-bipyridine (dtb-bpy)), (lut)₂Zn₃(μ₂,η²-OOCR)₂(μ₂-OOCR)₄ (1), [(phen)₂Zn₃(μ₂,η²-OOCR)₂(μ₂-OOCR)₄]·2MeCN··2C₆H₆ (2), and (dtb-bpy)₂Zn₃(μ₂,η²-OOCR)₂(μ₂-OOCR)₄ (3) (RCOO⁻ is the anion of β-naphthoic acid C₁₀H₇COOH), were synthesized. The structures of compounds 1–3 were studied by single-crystal X-ray diffraction. In the crystal structures, molecules 1–3 are ordered due to the coplanar arrangement of the aromatic substituents of the acid and the N-donor ligands, as well as through stacking interactions.     

Synthesis,Characterization and Crystal Structure of a Trinuclear Diorganotin(Ⅳ) Complex with N'-acetylsalicylhydrazide

A diorganotin(IV) complex [(CH3)2Sn]3L2(L=N'-acetylsalicyl-hydrazide) 1 has been successfully synthesized and structurally characterized by elemental analysis,FT-IR,NMR(1H,13C and 119Sn) spectra and X-ray crystallography.The crystal structure belongs to an orthorhombic system,space group Pnma with a=8.5047(16),b=28.466(5),c=12.842(2) ,V=3109.1(10)3,C24H32N4O6Sn3,Mr=828.61,Dc=1.770 g/cm3,μ(Mo-Kα)=2.432 mm-1,Z=4,F(000)=1608,the final R=0.0378 and wR=0.0973 for 2125 observed reflections(Ⅰ 2σ(Ⅰ)).The complex is a trinuclear organotin(Ⅳ) containing five-and six-coordinated tin atoms.And weak but significant Sn···O intermolecular interactions lead to the assembly of complex into a 1D linear polymeric chain supramolecular framework.     

Metal Complexes of Donor-functionalized Fluorinated β-Ketoiminates – Synthesis,Structure, and CVD Application

Six alkali metal complexes of partly-fluorinated, donor-functionalized β-ketoiminate ligands [L¹Li ( 1 ), L¹Na ( 2 ), L¹K ( 3 ), L¹Cs ( 4 ), L¹ = OC(CF₃)CHC(CH₃)NCH₂CH₂OCH₃; L²Li ( 5 ), L²Na ( 6 ), L² = OC(CF₃)CHC(CH₃)NCH₂CH₂N(CH₃)₂] were prepared and structurally characterized. Reactions of L¹Li with PtCl₂ gave the homoleptic Pt complex L¹₂Pt ( 7 ), which was characterized spectroscopically and by single-crystal X-ray diffraction and whose promising application as CVD precursor (chemical vapor deposition) is shown. Polycrystalline, pure Pt films were grown at 500 °C on SiO₂@Si(100) substrates at 10^–3 mbar and characterized by XRD, SEM, AFM, EDX and XPS.     

Structure of Trinuclear Cadmium Complex with Acetato and Pyridine Ligands

1INTRODUCTIONItisnotedthatmetallothionien(MT)canspecificallycollectheavymetalssuchascadmiumandmercury,butthismettaloproteinisonlyacquiredfrominductiveeffect'illAsmodelsofthepeptidechainsofMT,recentlyanumberofdinucle-inorganism.AsmodelsofthepeptidechainsofMT,recentlyanumberofdinucle-atingSchiffbaseligandswithorwithoutsulphurdonorwassuccessfullyusedtopre-paretrinuclearcadmiumcomplex("31.Ontheotherhand,somemononuclearcadmi-umcomplexeswereformedwhensmallorganicfig'andssuchaspyridinemolecu…