新型含吡咯亚胺基辅助配体的金属铱(III)配合物的 合成、表征及发光性质

合成了一系列含有吡咯亚胺基为辅助配体的2-苯基吡啶铱配合物[(ppy)2Ir(N^N)] (ppy＝2-苯基吡啶), 通过1H NMR, MS, HRMS和元素分析对配合物结构进行了表征, 并研究了合成配合物的反应条件、紫外吸收光谱、光致发光光谱及铱配合物荧光量子产率. 结果表明, 在无水乙酸钠、二氯甲烷溶液中, 室温反应12 h可获得较高的产率. 通过改变吡咯亚胺类配体中的取代基, 该类配合物在507～606 nm之间具有不同的发光波长, 实现了从绿光到红光的转变. 所有的铱配合物在二氯甲烷溶液(空气中)表现出较高的量子效率(0.25～0.95).     

两个双核铁（Ⅲ）和三足配体的配合物的合成和晶体结构

运用三足四齿配体三（2－甲基吡啶）胺（TPA）或三（2－甲基苯丙咪唑）胺（TBA）,得到两个双核铁(III)配合物，[Fe₂L₂(μ₂-O)(μ₂-p-NH₂-C₆H₄COO)]³⁺ (L = TPA, 1 和 L = TBA, 2)。两个配合物均为单斜晶系，空间群为P2(1)/c.晶胞参数 1: a = 1.4529(4), b = 1.6622(5), c = 2.0625(6) nm, β= 100.327(5)º, V = 4.900(3) nm³, z = 4, F(000) = 2344, 分子量M_r = 1142.91, Dc = 1.549 g/cm³, R₁ = 0.0544, R₂ = 0.0962. 2: a = 1.3378(4), b = 2.1174(7), c = 2.4351(7) nm, β= 97.315(6)º, V = 6.842(4) nm³, z = 4, F (000) = 3116, 分子量M_r = 1505.08, Dc = 1.444 g/cm³, R₁ = 0.0793, R₂ = 0.1623. 在两个双核铁(III)配合物中，中心的三价铁和配体TPA或TBA上的四个氮原子和两个氧原子通过不同的桥形成一个畸变的八面体构型。     

Synthesis,Characterization, Crystal Structures and Antimicrobial Activity of Oxidovanadium(V) Complexes with Mixed Ligands

Russian Journal of Coordination Chemistry - Two new oxidovanadium(V) complexes, [VOLL1] (I) and [VOLL2] (II), where L is the dianionic form of the hydrazone ligand...     

Synthesis,Characterization, Antibacterial and Antifungal Activity of Yttrium(III) Complexes Including 1,10‐Phenanthroline

Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)₂(NO₃)₃ and (phenH)₂[Y₂(pydc)₃(NO₃)₂·6H₂O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH⁺)₂(pydc^2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.     

Cyclometalated Iridium(III) and Rhodium(III) Complexes Containing Naphthyridine Ligands: Synthesis,Characterization and Biological Studies

The synthesis, crystal structure, and biological activity of new bis‐cyclometalated compounds [M(ptpy)₂(4‐chloro‐2‐methyl‐1,8‐naphthyridine)]PF₆ [M = Rh ( 1 ); M = Ir ( 2 ); ptpy = 2‐(p‐tolyl)pyridinato] and [M(ptpy)₂(2‐methyl‐1,8‐naphthyridine)]PF₆ [M = Rh ( 3 ); M = Ir ( 4 )] are described. The new compounds were prepared by the reaction of [{M(μ‐Cl)(ptpy)₂}₂] (M = Rh, Ir) with the corresponding naphthyridine ligands. The molecular structures of compounds 1 , 3 , and 4 were confirmed by single‐crystal X‐ray diffraction studies.     

Oxygenation of Co(II) Complexes with Tripodal Ligands

The kinetics of O₂-uptake of five-coordinated Co²⁺/tren complexes (tren = 2,2′, 2″-tris(2-aminoethyl)amine) have been studied extensively. The kinetics of formation of (tren)Co(O₂, OH)Co(tren)³⁺ exhibits two steps. The rate law of O₂-addition, the first step, was of the form: rate = (k[H⁺] + kK_a)/([H⁺] + K_a) [Co(tren)²⁺][O₂]. Second-order rate constants k = 220 ± 19 M ^?1s^?1 and k = 1.8 ± .035 · 10³M ^?1s^?1 agreed well from O₂-uptake and (stopped-flow) spectrophotometric measurements. The protonation constant of the hydroxo complex obtained by equlibrium measurements (spectrophotometric and by pH-titration) in anaerobic conditions (pK_a = 10.03) agreed well with that derived from kinetic data (p K_a = 9.93); k and k are about a factor 100 smaller than those for the pseudooctahedral Co(trien) (H₂O). This and the fact that several other Co(II) complexes with five-coordinated geometry do not exhibit oxygen affinity led to the proposal that the oxygenation mechanism for Co²⁺/tren complexes involves fast preequilibria between Co(tren) (H₂O)²⁺ and Co(tren) (H₂O) and only the latter is assumed to be reactive. The enhanced rate at high pH is explained by rate determining H₂O-exchange in the O₂-addition step and the ability of coordinated OH^? to labilize the neighbouring H₂O. This mechanism is furthermore supported by the formation of one kinetically preferred isomer of the peroxo-bridged dicobalt(III) complex (O₂ cis to the tertiary N-atom) and the large negative activation entropy (?30 eu). The second step is the intramolecular bridging reaction: is independent of [Co(tren)²⁺] and [O₂] but exhibits a pH-dependence of the form k₃ = k′₃[H + ]/(K_a + [H⁺]); k_?3 ( = 5 · 10^?5 s^?1) was determined independently and from the two rate constants the equilibrium constant was calculated as ≈ 10⁵. The ligand combination as in Co(tren)²⁺ was shown to provide an excellent balance to form a reversible oxygen carrier; possible reasons for this are discussed.     

Synthesis,Characterization, and Anti-Diabetic Therapeutic Activity of New Vanadyl(II) Complexes with Orotic Acid and Different Amino Acids Mixed Ligands

Russian Journal of General Chemistry - Mixed ligand vanadyl(II) complexes of orotic acid and six different amino acids (isoleucine, threonine, proline, phenylalanine, lysine, and glutamine) have...     

Synthesis and Characterization of Some Mixed Ligand-Selenito and Tellurito Chromium(III) Complexes

New mixed ligand Cr(III) complexes were prepared where diamine or oxalato ligands are coordinated together with either tellurito, selenito, or hydrogenselenito ions to form nine octahedral complexes. The complexes were characterized by chemical analyses, IR and UV-visible spectra, magnetic, and conductivity measurements. The tellurito and selenito ligands act as monodentate ligands, coupled with the bidentate diamine ligands. On the other hand, they act as bidentate chelate ligands when coordinated together with the oxalate ligand. However, hydrogenselenite ion act as a monodentate ligand coupled with the oxalate ligand. IR spectra indicated that the inorganic ligands are coordinated to the Cr(III) ion through their oxygen atoms. One of the bulky diamine molecules, 1,2-pn or 1,3-pn, was freed from the coordination sphere of Cr(III) on the addition of the bulky inorganic anions and was replaced by two water molecules.     

Synthesis,Characterization, and Magnetic Properties of Iron Complexes Bearing Polydentate Nitrogen Ligands

Four iron complexes {[PhN(CH₂)₂NH(SiMe₃)]₄FeLi · Et₂O ( 1 ), [PhN(CH₂)₃NSiMe₃]₂FeLi(Et₂O) ( 2 ), [PhN(CH₂)₂NCH(Ph)NSiMe₃]₂FeLi(Et₂O)₂ ( 3 ), and [PhN(CH₂)₃NCH(Ph)NSiMe₃]₂FeLi(Et₂O)₂ ( 4 )} with polydentate nitrogen ligands were synthesized and structurally characterized by X‐ray crystallography. The X‐ray structures of complexes 1 – 4 show that they crystallize in three different systems. The magnetic properties of 1 – 4 were investigated. The magnetization trends of magnetic field intensity show the curves of Type‐S, illustrating those complexes 1 – 4 are superparamagnetic.     

含混合配体多酸超分子化合物的水热合成、晶体结构及催化活性

在水热条件下合成了四个含混合配体4,4’-bipy和2,2’-bipy/phen的多酸配位聚合物[Cu(4,4’-bipy)(2,2’-bipy)2]2[SiW12O40]?4H2O (1),[Ag4(4,4’-bipy)3(2,2’-bipy)2][SiW12O40]?2H2O (2),[Cu(4,4’-bipy)(phen)]2[H3O]2[SiW12O40]?8H2O (3)和[Cu(4,4’-bipy-Cl)(phen)]2[H3O][PW12O40]?H2O (4) (bipy = 联吡啶,phen = 邻菲罗啉),通过红外光谱、热重、元素分析、X-单晶衍射对聚合物进行了表征,在苯乙烯催化环氧化反应中,3和4显示了较高的催化活性,这与结构中存在配位不饱和金属中心有关.     

Cyclometalated Iridium(III) Complexes Containing Semicarbazone Ligands: Synthesis,Characterization, Photophysical and Biological Studies

The synthesis, crystal structure, photophysical properties, and biological activity of the novel bis‐cyclometalated complexes [Ir(ptpy)₂(vnsc)] ( 2 ) and [Ir(ptpy)₂(acsc)] ( 3 ) [ptpy = 2‐(p‐tolyl)pyridinato, vnsc = vanillin semicarbazone, acsc = acetone semicarbazone] are described. The new compounds were prepared by the reaction of [{Ir(μ‐Cl)(ptpy)₂}₂] ( 1 ) with the corresponding semicarbazone ligands under basic conditions. The molecular structure of compound 3 was confirmed by a single‐crystal X‐ray diffraction study. The complex crystallized from chloroform as a mono‐ solvate in the orthorhombic space group Pcab with eight molecules in the unit cell.     

Biological and Catalytic Applications of Pd(II)-Indenyl Complexes Bearing Phosphine and N-Heterocyclic Carbene Ligands

A general synthetic entryway into novel cationic Pd(II) indenyl complexes bearing one alkyl/aryl phosphine and one N-heterocyclic carbene is reported. All metal complexes have been exhaustively characterized by spectroscopic and structural analyses, highlighting that the indenyl fragment has an hapticity intermediate between η³ and η⁵. Most of the target complexes are stable in solid state and in solution for a long time. Two different applications of these organopalladium compounds are proposed. Firstly, they have been tested as antiproliferative agents towards three different ovarian cancer cell lines, showing a cytotoxicity significantly higher than that of cisplatin, with a clear dependence on the nature of the coordinated phosphine. Moreover, the similar cytotoxicity towards cisplatin-sensitive and cisplatin-resistant cell lines suggests that these new palladium derivatives act with a different mechanism of action with respect to classical platinum-based drugs. Finally, the water-soluble palladium complexes bearing 1,3,5-triaza-7-phosphaadamantane (PTA) have demonstrated interesting catalytic performances in Suzuki–Miyaura coupling in aqueous media, being, inter alia, readily and efficiently recyclable.     

Vanadium(III) Complexes of Oxygen Donor Ligands; Their Synthesis,Spectral Characterization and Antimicrobial Studies

A new series of vanadium(III) complexes with oxygen donor ligands have been synthesized and characterized on the basis of elemental analysis, conductance, infra‐red spectroscopy, electronic spectral data and mass spectrometry. Thermal stabilities of the complexes and their kinetics were studied through thermogravimetric analysis. Estimation of vanadium in the complexes is carried out by ICP‐AES. Biological activities of the complexes 2 – 5 , 7 and 8 have also been tested against various bacteria and fungi.     

Structures and Properties of Novel Mononuclear Iron(III) Complexes with Benzimidazole Containing Tripodal Tetradentate Ligands

The iron(III) complexes of the tripodal benzimidazole‐containing ligands tris(2‐benzimidazolylmethyl)amine (ntb), bis(2‐benzimidazolylmethyl)(2‐hydroxyethyl)‐amine (bbimae) and tris(5,6‐dimethyl‐2‐benzimidazolylmethyl)amine (me₂ntb) are structural and functional models for intradiol cleaving catechol dioxygenases. The complexes [Fe(ntb)Cl₂]Cl · 3 CH₃OH ( 1 ; P 1, a = 9.830(2) Å, b = 12.542(3) Å, c = 13.139(3) Å, α = 82.88(3)°, β = 73.45(3)°, γ = 85.53(3)°, V = 1539.2(6) ų; Z = 2) and [Fe(bbimae)Cl₂]Cl ( 2 ; P2₁/n, a = 7.461(2) Å, b = 18.994(5) Å, c = 14.515(4) Å, β = 98.22(2)°, V = 2035.8(9) ų, Z = 4) have been characterized by X‐ray crystallography and spectroscopic methods. In the octahedrally coordinated complexes two cis coordination sites – essential for catechol binding – are occupied by chloride ligands. The significant intradiol cleaving catechol dioxygenase activity of the model complexes was examined using 3,5‐di‐tert‐butylcatechol as a substrate.     

Macrocyclic Metal Complexes Bearing Rigid Polyaromatic Ligands: Synthesis and Catalytic Activity

We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes.     

Cerium(IV) Nitrate Complexes With Bidentate Phosphine Oxides

The reactions between ceric ammonium nitrate, (NH₄)₂Ce(NO₃)₆, (CAN) and the bidentate phosphine oxides, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene (L¹), oxydi-2,1-phenylene bis(diphenylphosphine dioxide) (L²), 1,2-bis(diphenylphosphino)ethane dioxide (L³) and 1,4-bis(diphenylphosphino)butane dioxide, L⁴ have been investigated. The crystal structures of the molecular Ce(NO₃)₄L¹ ( 1 ), and ionic [Ce(NO₃)₃L³₂][NO₃]⋅CHCl₃ ( 3 ), [Ce(NO₃)₃L³₂][NO₃] ( 4 ) and the polymeric [Ce(NO₃)₃L⁴_1.5] [NO₃] ( 5 ) and the cerium(III) complex [Ce(NO₃)₂L¹₂][NO₃] ( 2 ) are reported. The thermal stability of the complexes has been examined by thermogravimetry with the gaseous decomposition products analysed by infrared spectroscopy. Evolution of CO₂ is found for both Ce(III) and Ce(IV) complexes with the later also forming NO₂. The formation of the complexes in solution has been studied by ³¹P NMR spectroscopy and further complexes [Ce(NO₃)₃L¹₂]⁺[NO₃]⁻ and [Ce(NO₃)₂L¹₃]²⁺2[NO₃]⁻ identified in CD₃CN solution. The complex ( 1 ) exists as a single molecular species in solution and is stable in dichloromethane whilst ( 3 ) decomposes on standing in both CD₂Cl₂ and CD₃CN to Ce(III) containing species. Complexes of L² have been identified by solution ³¹P NMR spectroscopy and these decompose in solution to give Ce(NO₃)₃L²₂. This study represents the first structural characterisations of Ce(IV) complexes with bidentate phosphine oxides.     

Synthesis and Characterization of Novel Orange-emitting Iridium(III) Complexes with Diphenylquinoline Ligands Containing Fluorinated Substituent

Recently, the iridium complexes as phosphorescent emitter in organic light-emitting diodes (OLEDs) have attracted much attention since the realization of a high efficiency OLED device based on the complex fac tris(2-phenylpyridine)iridium [Ir(ppy)3]1-4. T…     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.