Novel Ag ion-selective electrodes based on two new mixed azathioether crowns containing a 1,10-phenanthroline sub-unit

Novel polymeric membrane (PME) and coated graphite (CGE) silver-selective electrodes based on two recently synthesized mixed azathioether crowns containing a 1,10-phenanthroline sub-unit were prepared. The electrodes reveal a Nernstian behavior over quite wide Ag⁺ ion concentration ranges with a very low limits of detection (LOD) (i.e. down to 1.0×10⁻⁸ M for CGEs and 8.0×10⁻⁷ M for PMEs). The potentiometric responses are independent of the pH of the test solution in the pH range 3.0-7.0. The electrodes possess advantages of low resistance, very fast response time, relatively long lifetimes and, especially, good selectivities relative to a wide variety of other cations. The electrodes were used, as indicator electrodes, in the potentiometric titration of silver ion and in the determination of Ag⁺ in waste water, photographic emulsion and radiographic and photographic films.     

Synthesis and magnetic properties of novel containing 1,10-phenanthroline polymeric complexes

The polymer (DAPcTPA) was synthesized by polycondensation of 5,6-diamine-1,10-phenanthroline (DAP) with terephthaldehyde (TPA). Three polymeric complexes were first prepared from polymer (DAPcTPA) and NiSO₄, CoCl₂ or FeSO₄, respectively. The structures of polymer and complexes were characterized by IR, ¹H NMR spectra and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength (0-50 kOe) at 5 K and as a function of temperature (5-300 K) at a magnetic field strength of 30 kOe. The results show that DAPcTPA-Ni²⁺ and DAPcTPA-Co²⁺ are soft ferromagnets, while DAPcTPA-Fe²⁺ exhibits features of an antiferromagnet.     

Three new lanthanide coordination polymers containing isophthalate and 1,10-phenanthroline

Three lanthanide coordination polymers were prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. [Pr₂(mBDC)₃(phen)(H₂O)]_n·0.5nH₂O (1) (mBDC=isophthalate, phen=1,10-phenanthroline) exhibits two kinds of metal environments (coordination numbers 7 and 8). In complex 1, mBDC ligands adopt the tetradentate (bridging and bridging) coordination mode and connect Pr ions into an undulating layer, and a 3D supramolecular structure is formed via hydrogen bonds between adjacent layers. [Tb₄(mBDC)₆(phen)]_n (2) has three types of metal environments (coordination numbers 6, 7 and 8) and is composed of a 3D network formed by mBDC linking Tb ions via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. There are two kinds of small quadrilateral channels along the a-axis. [Er₄(mBDC)₆(phen)]_n (3) is isostructural to complex 2.     

Copper(II)-selective membrane electrodes based on some recently synthesized mixed aza-thioether crowns containing a 1,10-phenanthroline sub-unit

Three different mixed aza-thioether crowns containing a 1,10-phenanthroline sub-unit were investigated to characterize their abilities as copper(II) ion carriers in PVC-membrane electrodes. The electrode based on L1 exhibited a Nernstian response for Cu²⁺ ions over a wide concentration range (2×10⁻¹ to 1×10⁻⁵ M) with a limit of detection of 8.0×10⁻⁶ M (0.5 p.p.m.). The response time of sensor is 15 s, and the membrane can be used for more than 3 months without observing any deviation. The electrode revealed comparatively good selectivities with respect to many alkali, alkaline earth, transition and heavy metal ions, and could be used in a pH range of 2.5–5.5. It was applied to the direct determination and potentiometric titration of the copper(II) ion.     

Synthesis,structure, and luminescent properties of lanthanide complexes containing 1,10-phenanthroline and perfluorinated 2-mercaptobenzothiazolate ligands

Mononuclear terbium and erbium complexes of the composition Ln(mbt^F)₃phen and the dinuclear complex Tb₂(mbt^F)₄(OH)₂(phen)₂ (mbt^F is 4,5,6,7-tetrafluoro-2-mercaptobenzothiazolate, phen is 1,10-phenanthroline) were synthesized. The structures of the complexes Er(mbt^F)₃phen and Tb₂(mbt^F)₄(OH)₂(phen)₂ were determined by X-ray diffraction. In the solid state, the terbium and erbium complexes exhibit intense metal-centered photoluminescence. Based on the complexes Ln(mbt^F)₃phen, double-layer organic light-emitting diodes (OLEDs) were assembled. These OLEDs exhibit electroplex emission with a band maximum at 630 nm.     

Synthesis and coordination properties of highly preorganised polyamine macrocycles

Synthesis and characterisation of the new macrocyclic ligands L1‐L4 are reported. The ligands present one or two pentaamine moieties, each containing two piperazine rings, linked by benzene or anthracene spacers. Interaction of L1 with H⁺, Cu(II), Zn(II), Hg(II), and Pd(II) and of L3 with H⁺, and Cu(II) has been studied by potentiometric titrations in 0.15 mol dm^?3 NaCl aqueous solution at 298.1 ±0.1 K. The thermodynamic data suggest that in the metal complexes only three nitrogen donor atoms bind each metal ion. As a consequence of the low coordination number, these complexes are promising receptors for different molecules.     

Synthesis of an oblique bis-porphyrin system containing a 1,10-phenanthroline spacer

A molecule consisting of two porphyrin rings (free base or Zn complex) rigidly held by a 1,10-phenanthroline nucleus has been made; the centre-to-centre separation is about 13Å.     

Synthesis of 5-isothiocyanato-1,10-phenanthroline

Reduction of 5-nitro-1,10-phenanthroline with hydrogen over Pd/C, followed by the treatment of 1,10-phenanthrolin-5-amine with thiophosgene in the presence of sodium acetate, gave 5-isothiocyanato-1,10-phenanthroline which is a thermally stable highly reactive ligand capable of quantitatively forming covalently bonded nanohybrid structures in a system transition metal complex-silica under mild conditions.     

4,7-二苯基-1,10-菲啰啉的合成研究

以4-苯基-8-硝基喹啉为起始原料,经还原得到4-苯基-8-氨基喹啉,再以I2/KI为氧化剂,在乙酸和盐酸的存在下,用Skraup法合成了4,7-二苯基-1,10-菲啰啉.化合物结构经IR和1H NMR得到了证实.实验研究得到了最佳的合成条件为:n(3-氯苯丙酮)∶n(4-苯基-8-氨基喹啉)=1.5∶1,I2/KI用量为8%,反应温度120℃,反应时间2.5 h.产品收率可达82%.     

Synthesis of new dibenzo nitrogen-oxygen donor macrocycles containing two amide groups

Four new nitrogen-oxygen, dibenzo macrocyclic ligands containing two amide groups have been prepared by combining a dibenzo-containing diamidodialdehyde with an appropriate diamine followed by reduction of the intermediate bis Schiff-base. The starting dibenzo-containing diamidodialdehyde was prepared by treating 2 equivalents of salicylaldehyde with a bis(α-chloroamide).     

1-D Chain lanthanide coordination polymers based on mixed 2,4-dichlorophenoxyacetate and 1,10-phenanthroline ligands: crystal structures and luminescent properties

Two new isostructural 1-D lanthanide coordination polymers, {[Ln(2,4-dcp)₃(phen)] _n [(Ln?=?Eu (1); Tb (2)], [2,4-dcp?=?2,4-dichlorophenoxyacetate, phen?=?1,10-phenanthroline], were obtained under hydrothermal conditions and characterized by IR spectroscopy, elemental analyses, thermogravimetry analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. Both structures exhibit similar 1-D infinite chains with a {Ln₂(2,4-dcp)₆(phen)₂} dimeric repeat unit, with lanthanides in an eight-coordinate environment. The results of thermal analysis indicate that 1 and 2 are quite stable to heat. 3-D fluorescence spectra of 1 and 2 were detected at room temperature under excitation and the emission wavelengths of 250–460?nm and 420–750?nm with the same interval of 5?nm, respectively. Interestingly, 1 and 2 possess longer fluorescence lifetimes than other complexes (τ?=?1.61?ms for 1 at 611?nm; 1.79?ms for 2 at 543?nm).     

Synthesis of some novel heteroarylene ethynylene polymers containing 1,10-phenanthroline in the polymer backbone

Palladium-catalyzed polycondensation between 3,8-dibromo-1,10-phenanthroline and substituted phenyl-1,4-diacetylenes in the presence of diisopropylamine produced the soluble π-conjugated poly(heteroarylene ethynylene)s 7a and 7b . The polymers were obtained in high yields (86–92%) and had molecular weights of M̄_n = 8700 g · mol⁻¹ ( 7a ; vapor pressure osmometry) and 6900 g · mol⁻¹ ( 7b ; vapor pressure osmometry). The low molecular model compounds 6a and 6b were prepared to analyze the connection between the primary structure and spectroscopic properties. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4442–4448, 1999     

Synthesis,structures and properties of ternary rare earth complexes with fluorobenzoic acid and 1,10-phenanthroline

Three dimeric rare-earth complexes [Eu(p-FBA)₃(phen)(H₂O)]₂ (1), [Tb(p-FBA)₃phen]₂ (2), and [Tb(o-FBA)₃phen]₂ (3) (where p-FBA = p-fluorobenzoate, o-FBA = o-fluorobenzoate, phen = 1,10-phenanthroline) were synthesized and structurally characterized. All are neutral dimeric molecules. Complex 1 crystallizes in triclinic system, space group P 1. Each Eu(III) ion is eight-coordinate with one 1,10-phenanthroline, one monodentate carboxylate, one water and four bridging carboxylates. Complex 2 crystallizes in triclinic system, space group P 1. Each Tb(III) is also eight-coordinate with one 1,10-phenanthroline molecule, one bidentate chelating carboxylate and four bridging carboxylates. Complex 3 crystallizes in the monoclinic system, space group P2₁/c and consists of two crystallographically different binuclear molecules. Tb(III) ions are eight-coordinate with one 1,10-phenanthroline, one bidentate chelating carboxylate and four bridging carboxylates in both of them. Complex 1 shows bright red luminescence, 2 and 3 show green luminescence under UV light at room temperature. Thermal analysis indicates that are all quite stable to heat.     

Synthesis, crystal structure and properties of two 1D nano-chain coordination polymers constructed by lanthanide with pyridine-3,4-dicarboxylic acid and 1,10-phenanthroline

The hydrothermal reactions of LnCl₃·6H₂O (Ln=Eu, Tb), pyridine-3,4-dicarboxylic acid (3,4-pydaH₂), 1,10-phenthroline (phen) and NaOH in aqueous medium yield two metal-organic hybrid materials, [Eu₂(3,4-pyda)₃(phen)(H₂O)·H₂O]_n (1) and [Tb₂(3,4-pyda)₃(phen)(H₂O)·H₂O]_n (2), respectively. Both compounds have similar topology structure containing one-dimensional nano-chain, which is further assembled into a three-dimensional supramolecular network via π-π stacking interactions and hydrogen bonds. To the best of our knowledge, they represent the first example of nano-chain coordination polymers constructed by 3,4-pydaH₂ and chelate heterocylic ligand. Interestingly, the 3,4-pyda anion exhibits three kinds of coordination modes in these complexes. The coordination modes of 3,4-pyda in complexes 1 and 2 have not been observed in other coordination polymers containing 3,4-pyda ligands. Compounds 1 and 2 exhibit strong fluorescent emission bands in the solid state at room temperature. Their magnetic analyses show that they exhibit different magnetic interactions.     

Iron(II) and nickel(II) mixed-ligand complexes containing 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline

Two types of mixed-ligand complexes, i.e. [M(phen)2 (dip)]2+ and [M(phen)(dip)2]2+ (M = iron(II) and nickel(II); phen = 1,10-phenanthroline and dip = 4,7-diphenyl-1,10-phenanthroline) have been prepared from their related tris-complexes, [M(phen)3]2+ by ligand substitution, and isolated by semi-preparative HPLC. Elemental and chromatographic analyses confirm the purity of the isolated complexes while u.v./vis and i.r. spectra were used to identify and characterize them. 1H-n.m.r. and room temperature Mössbauer spectra of the iron(III) complexes were also measured and the results are discussed. In addition, our preliminary results on hypochromicity in the MLCT band and circular dihroism (CD) emerging in the u.v./vis region upon addition of CT(calf thymus)-DNA to the racemic complexes indicated that the iron(II) mixed-ligand complexes interact with CT-DNA.     

Spectral properties and analytical application of the ternary complex of lanthanum(III) with 1,10-phenanthroline and eosin

The pink lanthanum—(1,10-phenanthroline)₂—(eosin)₂ complex is used to determine 0.5–10 × 10^-5 M lanthanum, either in aqueous solution or chloroform. In the presence of EDTA, only aluminium and cyanide interfere.     

稀土配合物的研究 I: 镧系元素与4-酰代-双吡唑啉酮及1,10-二氮杂菲的混配配合物的合成及表征

用镧系硝酸盐与1,6-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)-1,6-己二酮(1,H2L)和1,10-二氮杂菲(2, Phen)在乙醇-水溶液中, 于PH5-6时合成了12种新的固态配合物Ln2L3Phen2. 4H2O(Ln=Pr, Nd, Sm-Lu)。用元素分析、水份及配体分析、红外、紫外,质子核磁共振、荧光光谱和热分析鉴定了所有的配合物, 从而推测, 可能L是四啮配体,Phen是二啮配体。     

铒(Er)-L-组氨酸-邻菲啰啉三元配合物的合成与性质

在乙醇介质中,合成了铒(Er)-组氨酸(L-His)-邻菲啰啉(Phen.H2O)三元稀土配合物,利用摩尔电导率、络合滴定分析、元素分析、红外光谱(IR)和热重-差热(TG-DTA)等分析测试,推测配合物的化学组成为:[Er(L-His)3Phen]Cl3.3H2O。初步研究了配合物的电化学性质和生物活性;其中稀土配合物对革兰氏阴性菌大肠杆菌、革兰氏阳性枯草芽孢杆菌都有较好的抑制作用,特别是对革兰氏阴性菌大肠杆菌抑制效果更好。并通过循环伏安测定了配合物在铂盘工作电极上的电化学行为,在HAc-NaAc缓冲溶液(pH≈6.0)中ErCl3.6H2O和配合物{[Er(L-His)3Phen]Cl3.3H2O}在-0.3 V～-1.0 V(vs.SCE)电位范围内均表现出电化学活性,配合物的电化学活化中心是Er3+,该配合物为准可逆体系,且配合物的还原峰电流与浓度和扫描速率呈现递增关系。