Mono and trinuclear lanthanide complexes of 13-membered tetraaza macrocycle: Synthesis and characterization

The reaction of 1,8-diamino-3,6-diazaoctane and diethyl malonate in dry methanol yielded a 13-membered macrocycle. Complexes of the type [Ln(tatd)Cl₂ (H₂O)₃]Cl [Ln^III=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy; tatd=1, 5, 8, 11-tetra-azacyclotridecane-2,4-dione] have been synthesized by template condensation. The complex [La(tatd)Cl₂ (H₂O)₃]Cl in methanol was reacted with lanthanide chlorides to yield the trinuclear complexes of type [2{La(tatd)Cl₂(H₂O)₃}LnCl₃]Cl₂ [Ln^III=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy]. The chemical compositions of mono and trinuclear complexes have been established on the basis of analytical, molar conductance, electrospray (ES) and fast atom bombardment (FAB) mass data. In mononuclear complexes the Ln³⁺ ion is encapsulated by four ring nitrogens and in trimetallic complexes the exo-carbonyl oxygens of two mononuclear units coordinate to the Ln³⁺ ions resulting in a polyhedron around the lanthanide ions. Thus the macrocycle is bonded in a tetradentate fashion in the former complexes and hexadentate in the latter. The coordination number nine around the encapsulated Ln³⁺ and seven around the exo-oxygen bonded Ln³⁺ ions are established. The symmetry of the ligand field around the metal ions is indicated from the emission spectra.     

Chelating behaviour of new 12-membered Schiff base macrocycles containing pendant groups

Summary The free Schiff base macrocycles 1,4,7,10-tetraazacyclo-dodeca-5,6,11,12-tetraaminoacetic acid-4,6,10,12-tetraene (L¹), 1,4,7,10-tetraazacyclododeca-5,6,11,12-tetraamino-phenyl-4,6,10,12-tetraene (L²) and 1,4,7,10-tetraazacyclo-dodeca-5,6,11,12-tetraaminopyridyl-4,6,10,12-tetraene (L³) have been prepared by the reaction of oxamidediacetic acid, oxamidediphenyl and oxamidedipyridyl, respectively, with ethylenediamine. Their complexes with first row transition metal ions, of types [MLCl₂] and [MLCl₂]Cl, have also been prepared and characterized by physico-chemical and spectroscopic methods. The complexes of divalent metal ions are non-ionic while those of trivalent metal ions appear to be 11 electrolytes. An octahedral geometry is proposed for all the complexes.     

Synthesis and characterization of three heptaaza manganese(II) macrocyclic Schiff base complexes containing two 2-pyridylmethyl pendant arms

Three new Mn(II) bis(pendant arm)-macrocyclic Schiff base complexes, [MnLⁿ]²⁺(n = 1, 2, 3), have been prepared via cyclocondensation of 2,6-diacetylpyridine with three different branched hexadentate amines (3,6-bis(2-pyridylmethyl)-3,6-diazaoctane-1,8-diamine (1), 3,7-bis(2-pyridylmethyl)-3,7-diazanonane-1,9-diamine (2) and 3,8-bis(2-pyridylmethyl)-3,8-diazadecane-1,10-diamine (3)) in the presence of MnCl₂ in methanol. The ligands, L, are 15-, 16- and 17-membered pentaaza macrocycles having two 2-pyridylmethyl pendant arms [L¹; 2,13-dimethyl-6,9-bis(2-pyridylmethyl)-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18), 2, 12, 14, 16-pentaene, L²; 2,14-dimethyl-6,10- bis(2-pyridylmethyl)-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19), 2, 13, 15, 17-pentaene and L³; 2,15-dimethyl-6,11-bis(2-pyridylmethyl)-3,6,11,14,20-pentaazabicyclo[14.3.1]eicosa-1(20),2,14,16,18-pentaene]. All the complexes have been characterized by physicochemical and spectroscopic methods. The crystal structure of [MnL¹](ClO₄)₂·CH₃CN has been determined and indicates that in the solid state, the complex adopts a slightly distorted pentagonal bipyramidal geometry with the Mn(II) centre located within a pentaaza macrocycle with two 2-pyridylmethyl pendants coordinating in the axial positions.     

Synthesis and characterization of new copolyacrylates containing porphyrin units as pendant groups and their use as sensors

Novel copolyacrylates containing various molar ratios of 5,10,15‐tri[p‐(9‐methoxy‐triethylenoxy)phenyl]‐20‐(p‐acryloxyphenyl)porphyrin units in the chains have been synthesized, and their chemical structure was determined by NMR and MALDI‐TOF mass spectrometry. Sensing response of the synthesized copolymers has been tested for trifluoroacetic and hydrochloric acids and nitrogen dioxide analytes. The reported sensing data indicate that porphyrin units are interacting with analytes in a reversible fashion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and structural characterization of a fully conjugated macrocyclic tetraaza(14)-membered Schiff base and its bivalent metal complexes

A novel 14-membered macrocyclic Schiff base derived from 3-cinnamalideneacetoacetanilide and o-phenylenediamine acts as a tetradentate and strongly conjugated ligand to form a cationic solid complex with CuCl₂/NiCl₂/CoCl₂/ZnCl₂. The ligand and the complexes were characterized by the usual spectral and analytical techniques. The main i.r. band of the macrocyclic Schiff base was compared to that of its metal complexes. The C=N bands are shifted to the lower wave number. The cyclic voltammogram of the copper complex shows that the macrocyclic ligand is able to stabilize the copper(III) oxidation state. The e.s.r. spectra of the copper complex in DMSO solution at room temperature and liquid N₂ temperature were recorded and their salient features thoroughly discussed. The antimicrobial screening tests were also recorded and gave good results in the presence of metal ions in the ligand system.     

Synthesis and characterization of three new organotin complexes containing piperazine as a bidentate ligand

The reaction of dichlorostannanes R₂SnCl₂ (R=Me 1, Buⁿ 2) with piperazine ligand in molar ratio 1:2, in dry methylene dichloride, in an inert atmosphere leads to the synthesis of R₂Sn(C₄H₉N₂)₂(R=Me 1, Buⁿ 2). In a similar manner, The reaction between Ph₂SnCl₂ and piperazine in dry ethanol in molar ratio 1:1 produces [Ph₂Sn(C₄H₈N₂)]₂ (3). The yields of these new products were excellent and they have been fully characterized by FT-IR, UV–Vis, multinuclear (¹H, ¹³C, ¹¹⁹Sn) NMR spectroscopy and mass spectrometry, as well as elemental analysis. The spectroscopic results indicate that the piperazine ligand is coordinated to tin atom of organotin moieties, through the nitrogen atoms. Furthermore, the ligand behaves as a bidentate fashion in (1) and (2) and gives 1:2 substitution products, while in the complex (3) the two six-membered rings bind in bidentate-chelate forms between the two Sn atoms.     

Synthesis, structural characterization and electrochemical studies of new macrocyclic Schiff base containing pyridine head and its metal complexes

A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:13,14-tribenzo-9,12-dioksa-cyclopentadeca-1,5-diene was synthesized by reaction of 2,6-diaminopyridine and 1,2-bis(2-carboxyaldehyde phenoxy)ethane. Then, its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes were synthesized by the template effect by the reaction of 2,6-diaminopyridine and 1,2-bis(2-carboxyaldehyde phenoxy)ethane and Cu(NO₃)₂ · 3H₂O, Ni(NO₃)₂ · 6H₂O, Pb(NO₃)₂, Co(NO₃)₂ · 6H₂O, La(NO₃)₃ · 6H₂O, respectively. The ligand and its metal complexes have been characterized by elemental analysis, IR, ¹H and ¹³C NMR, UV-Vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements, mass spectra, and cyclic voltammetry. All complexes are diamagnetic and Cu(II) complex is binuclear. The Co(II) was oxidized to Co(III). The comparative electrochemical studies show that the nickel complex exhibited a quasi-reversible one-electron reduction process, while copper and cobalt complexes gave irreversible reduction processes in DMSO solution.     

Complexing mechanism of the lanthanide cations Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota)-characterization of three successive complexing phases: study of the thermodynamic and structural properties of the complexes by potentiometry, luminescence spectroscopy, and EXAFS

Complexation of the lanthanides Eu3+, Gd3+, and Tb3+ with 1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (dota) has been studied in solution by using potentiometry, luminescence spectrometry, and EXAFS. Three series of successive complexes were characterized by at least two of these methods: the immediate [LnHn(dota)](n-1)+** and intermediate [LnHn(dota)](n-1)+* complexes with 0 相似文献   

Synthesis, structural characterization, and electrophosphorescent properties of rhenium(I) complexes containing carrier-transporting groups

Two novel diimine rhenium(I) carbonyl complexes with the formula [Re(CO)(3)(L)Br], where L = 1-(4-5'-phenyl-1,3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1) and 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), have been successfully synthesized and characterized by elemental analysis, (1)H NMR, and IR spectra. Their electrochemical, photophysical, and electroluminescent behaviors, along with the X-ray crystal structure analysis of 2, are also described. White electrophosphorescent devices were fabricated using 1 and 2 as emitters. The devices based on carbazole-containing (hole-transporting group) 2 with the structure ITO/m-MTDATA (30 nm)/NPB (20 nm)/2:CBP (8%, 30 nm)/Bphen (20 nm)/Alq(3) (20 nm)/LiF (0.8 nm)/Al (200 nm) exhibit Commission Internationale de L'Eclairage coordinates of x = 0.34, y = 0.33 with a maximum brightness of 2300 cd/m(2) at 580 mA/cm(2). When a brightness of 1500 cd/m(2) appears at 230 mA/cm(2), the devices based on 10 wt % 2 still possess 56% of the maximum efficiency which appeared at 2.7 mA/cm(2). These performances are among the best reported for devices using Re(I) complexes as emitters. By comparison of the electroluminescent properties of the devices based on 1 and 2, we conclude that the introduction of the carbazole group into the ligand improves the performance of 1-doped devices.     

Synthesis and characterization of new cardo poly(bisbenzothiazole-urea)s containing bulky pendant groups

A series of novel rigid poly(bisbenzothiazole-urea)s (PBTUs III) containing bulky pendant groups were synthesized from 2,2-diaminodibenzothiazoles and aromatic diisocyanates conveniently in the mild condition. The inherent viscosity, solubility, thermal stability, morphology, mechanical and photophysical properties of them were investigated and compared in detail. The inherent viscosities were in the range of 0.58-0.73 dL/g. All of the polymers exhibited excellent solubility in various polar organic solvents. They also showed good thermal stability and mechanical properties. The decomposition temperatures at 10% weight loss were in the range of 368-431 °C in nitrogen. All the PBTUs III were amorphous. Tensile strength of PBTUs III showed the range from 85 to 98 MPa. Compared with poly(benzothiazole)s, all the PBTUs III had the larger optical bandgap and lower photoluminescence quantum yields.     

Hydrazone as complexing agent: Synthesis,structural characterization and biological studies of some complexes

This paper deals with the synthesis, magnetic, spectral, thermal, and biological studies of Ti(III), VO(IV), Cr(III), Mn(III), Fe(III), and Zr(IV) complexes with chelating hydrazone derived from 2-hydroxy-5-methylacetophenone and furoic acid hydrazide. The acid hydrazone synthesized is 2-hydroxy-5-methylace-tophenone-furoylhydrazone. The ligand has been characterized on the basis of IR and ¹H NMR spectra. The presence of water molecules and thermal stabilities of the complexes are also reported. Solid-state electrical conductivity was measured over a 313–410-K temperature range, and the compounds show semiconducting behavior. The new complexes have been screened for their antibacterial and antifungal activity, and they show higher activity than free ligands.     

The synthesis and characterization of ( E,E )-dioxime and its transition metal complexes containing 12-membered macrocycles linked to ferrocenyl-methyl groups

13,14-bis(Hydroxyimino)-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4, 7-diaza-1,10-dithiacyclododecine[13,14-g]-quinoxaline (H₂L) has been prepared from (E,E)-dichloroglyoxime and 12,13-diamino-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4,7-diaza-1,10-dithiacyclododecine which was synthesized from 12,13-dinitro-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]4,7-diaza-1,10-dithia cyclododecine. Mononuclear nickel(II) and copper(II) complexes of H₂L have a metal-ligand ratio of 1?:?2 and the ligand coordinates through two nitrogen atoms, as do most (E,E)-dioximes. The homotrinuclear [Cu(L)₂Cu₂(dipy)₂](NO₃)₂ compound coordinates to the other two copper(II) ions through deprotonated oximate oxygens and two 2,2′-dipyridyl as an end-cap ligand to yield the trinuclear structure. The ligand and its complexes have been characterized on the basis of ¹H, ¹³C NMR, IR and MS spectroscopy and elemental analyses.     

Rare-earth-metal-containing polymers. 5. Synthesis,characterization, and fluorescence properties of Eu3+-polymer complexes containing carboxylbenzoyl and carboxylnaphthoyl ligands

Partially 2-carboxylbenzoyl (1) and 3-carboxyl-2-naphthoyl (2) substituted polystyrene were prepared by the Friedel-Crafts reaction of polystyrene with corresponding dicarboxylic anhydrides. Europium (III) salts of (1) and (2) and the copolymer of 4-vinylbenzoyl 2′-carboxylbenzoate-di(2-benzoyl benzoate) and styrene (5) were prepared. Polymer (5) was prepared by the copolymerization of the Eu³⁺ salt of 4-vinylbenzoyl 2′-benzoate and 2-benzoylbenzoate (ratio 1:2) with styrene. The fluorescence emission intensity was measured on fine powder samples. The intensity of (5) increased linearly as the Eu content increased. However, for the 1 and 2 systems the intensity reached a maximum at a Eu content as small as 0.5 wt% and remained constant when further increases were made. This phenomenon was accounted for by steric hindrance and a decrease in the freedom of bond rotation, which prevent the formation of multiple coordination linkages between Eu³⁺ and the benzoate groups.     

Synthesis, structures, and luminescence properties of lanthanide complexes with structurally related new tetrapodal ligands featuring salicylamide pendant arms

To explore the relationships between the structures of ligands and their complexes, we have synthesized and characterized a series of lanthanide complexes with two structurally related ligands, 1,1,1,1-tetrakis{[(2'-(2-benzylaminoformyl))phenoxyl]methyl}methane (L(I)) and 1,1,1,1-tetrakis{[(2'-(2-picolyaminoformyl))phenoxyl]methyl}methane (L(II)). A series of zero- to three-dimensional lanthanide coordination complexes have been obtained by changing the substituents on the Pentaerythritol. Our results revealed that, complexes of the L(I) ligand, {Ln(4)L(I)(3)(NO(3))(12).nC(4)H(10)O}(infinity) (Ln = Nd, Eu, Tb, Er, n = 3 or 6)] show the binodal 3,4-connected three-dimensional interpenetration coordination polymers with topology of a (8(3))(4)(8(6))(3) notation. Compared to L(I), complexes of L(II) present a cage-like homodinuclear [Ln(2)L(II)(2)(NO(3))(6).2H(2)O].nH(2)O (Ln = Nd, Tb, Dy, n = 0 or 1) or a helical one-dimensional coordination {[ErL(II)(NO(3))(3).H(2)O].H(2)O}(infinity) polymer. The luminescence properties of the resulting complexes formed with ions used in fluoroimmunoassays (Ln = Eu, Tb) are also studied in detail. It is noteworthy that subtle variation of the terminal group from benzene to pyridine not only sensibly affects the overall molecular structures but also the luminescence properties as well.     

Synthesis,characterization, and thermal and dielectric properties of three different methacrylate polymers with zwitterionic pendant groups

The synthesis, characterization, thermal, and dielectric properties of three different zwitterionic methacrylates of the sulfobetaine type are presented. Diethylamine-ethyl-, 2-(diethylaminoethoxy)-ethyl-, and 2-(2-diethylaminoethoxy) ethoxy-ethyl-methacrylates were made to react with butanosultone to prepare monomers with variable flexibility. The flexibility of the lateral chain of the polymethacrylates decreased the glass transition temperature (T_g down to 300 K) of the polymers. A linear relationship between T_g and the number of carbon atoms was shown for these materials. X-ray diffraction and DSC experiments showed the formation of new ordered phases in these polymers, which inhibited their dipole conductivity. On heating, these phases were destroyed and values of conductivity of 10⁻⁷–10⁻³ S cm⁻¹ were obtained in the studied range of temperature. Variation of conductivity with temperature was established according to the Arrhenius equation. Dielectric properties exhibited a small deviation of the Debye type behavior, and β parameters of the Cole–Cole equations were calculated for the synthesized polymers. © 1997 John Wiley & Sons, Inc.     

Spectral and electrochemical characterization of bimetallic complexes of a novel 32-membered unsymmetrical [N<Subscript>12</Subscript>] macrocycle

Reactions of a 32-membered [N₁₂] macrocyclic ligand, L.2HClO₄ with metal salts MCl₃ (M=Cr or Fe) and MCl₂ (M=Co, Ni or Cu) have produced complexes of stoichiometries M₂LCl₄(ClO₄)₂ and M₂LCl₂(ClO₄)₂, respectively. However, reactions with [M(Ph₃P)₂Cl₂] (M=Co or Ni) and [(η⁵-C₅H₅)Ni(Ph₃P)I] follow a ligand substitution path resulting in products with stoichiometries M₂LCl₂(ClO₄)₂ and [(η⁵-C₅H₅)₂Ni₂L(ClO₄)₂], respectively. The mode of bonding and geometry of the complexes have been derived on the basis of i.r., ligand field spectral and magnetic susceptibility measurements. EPR of Cu^II complex shows anisotropy with , G < 4.0 and orbital reduction factor . Thermodynamic first ionic association constants (K₁) and the corresponding free energy change (ΔG) of complexes in DMSO have been determined and discussed. Cyclic voltammetric studies indicate the presence of a quasi-reversible redox couples Cr^III/II, Co^II/I, Ni^II/I, Ni^II/III and Cu^II/I in solutions suggesting flexible nature of the macrocyclic cavity.     

Mn2+ complexes with 12-membered pyridine based macrocycles bearing carboxylate or phosphonate pendant arm: crystallographic, thermodynamic, kinetic, redox, and 1H/17O relaxation studies

Mn(2+) complexes represent an alternative to Gd(3+) chelates which are widely used contrast agents in magnetic resonance imaging. In this perspective, we investigated the Mn(2+) complexes of two 12-membered, pyridine-containing macrocyclic ligands bearing one pendant arm with a carboxylic acid (HL(1), 6-carboxymethyl-3,6,9,15-tetraazabicyclo[9.3.1] pentadeca-1(15),11,13-triene) or a phosphonic acid function (H(2)L(2), 6-dihydroxyphosphorylmethyl-3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene). Both ligands were synthesized using nosyl or tosyl amino-protecting groups (starting from diethylenetriamine or tosylaziridine). The X-ray crystal structures confirmed a coordination number of 6 for Mn(2+) in their complexes. In aqueous solution, these pentadentate ligands allow one free coordination site for a water molecule. Potentiometric titration data indicated a higher basicity for H(2)L(2) than that for HL(1), related to the electron-donating effect of the negatively charged phosphonate group. According to the protonation sequence determined by (1)H and (31)P pH-NMR titrations, the first two protons are attached to macrocyclic amino groups whereas the subsequent protonation steps occur on the pendant arm. Both ligands form thermodynamically stable complexes with Mn(2+), with full complexation at physiological pH and 1:1 metal to ligand ratio. The kinetic inertness was studied via reaction with excess of Zn(2+) under various pHs. The dissociation of MnL(2) is instantaneous (at pH 6). For MnL(1), the dissociation is very fast (k(obs) = 1-12 × 10(3) s(-1)), much faster than that for MnDOTA, MnNOTA, or the Mn(2+) complex of the 15-membered analogue. It proceeds exclusively via the dissociation of the monoprotonated complex, without any influence of Zn(2+). In aqueous solution, both complexes are air-sensitive leading to Mn(3+) species, as evidenced by UV-vis and (1)H NMRD measurements and X-ray crystallography. Cyclic voltammetry gave low oxidation peak potentials (E(ox) = 0.73 V for MnL(1) and E(ox) = 0.68 V for MnL(2)), in accordance with air-oxidation. The parameters governing the relaxivity of the Mn(2+) complexes were determined from variable-temperature (17)O NMR and (1)H NMRD data. The water exchange is extremely fast, k(ex) = 3.03 and 1.77 × 10(9) s(-1) for MnL(1) and MnL(2), respectively. Variable-pressure (17)O NMR measurements have been performed to assess the water exchange mechanism on MnL(1) and MnL(2) as well as on other Mn(2+) complexes. The negative activation volumes for both MnL(1) and MnL(2) complexes confirmed an associative mechanism of the water exchange as expected for a hexacoordinated Mn(2+) ion. The hydration number of q = 1 was confirmed for both complexes by (17)O chemical shifts. A relaxometric titration with phosphate, carbonate or citrate excluded the replacement of the coordinated water molecule by these small endogenous anions.     

Synthesis, characterization, and luminescence properties of a new series of Eu3+-containing macrocycles

The synthesis and structural characterization of a series of neutral Eu(3+)-containing macrocyclic complexes, Eu(4)-Eu(7), are reported. The synthetic pathway herein allows for the size and functionality of the macrocycle to be tailored in one step from a common precursor (N,N' '-bis(p-isothiocyanatobenzylcarbamoylmethyl)diethylenetriamine-N,N'N' '-triacetic acid, (3) in high yield. The macrocyclic ligands 4-7 have within their structure a bis-amide derivative of diethylenetriaminepentaacetic acid (DTPA) functioning as the europium chelate that is bridged through thiourea groups by either a butyl (4), hexyl (5), octyl (6), or m-benzyl (7) linker. The two thiourea groups were designed into the host macrocycle to serve as hydrogen-bond donors to potential guest molecules that may alter the luminescence properties of the parent macrocycle. Characterization of the luminescence of Eu(4)-Eu(7) reveals an antenna effect from the ligand, and the luminescence lifetime data reveals the presence of one coordinated water molecule in aqueous solution.     

Synthesis, characterization and photoluminescence properties of CaSiO3:Eu3+ red phosphor

CaSiO3:Eu3+ (1-5 mol%) red emitting phosphors have been synthesized by a low-temperature solution combustion method. The phosphors have been well characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and optical spectroscopy. PXRD patterns reveal monoclinic CaSiO3 phase can be obtained at 900°C. The SEM micrographs show the crystallites with irregular shape, mostly angular. Upon 254 nm excitation, the phosphor show characteristic fluorescence 5D0→7FJ (J=0, 1, 2, 3, 4) of the Eu3+ ions. The electronic transition located at 614 nm corresponding to 5D0→7F2 of Eu3+ ions, which is stronger than the magnetic dipole transition located at 593 nm corresponding to 5D0→7F1 of Eu3+ ions. Different pathways involved in emission process have been studied. Concentration quenching has been observed for Eu3+ concentration>4 mol%. UV-visible absorption shows an intense band at 240 nm in undoped and 270 nm in Eu3+ doped CaSiO3 which is attributed to oxygen to silicon (O-Si) ligand-to-metal charge-transfer (LMCT) band in the SiO3(2-) group. The optical energy band gap is widened with increase of Eu3+ ion dopant.