Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline

Three new coordination polymers,namely [Zn（FDA）（phen）（H2O）·H2O]n（1）,[Cd（HFDA）（phen）2（NO3）]（2） and [Cd（FDA）（phen）]n（3）（H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline） have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2＋ ions are bridged by FDA2-as linkers to form one-dimensional（1D） chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional（3D） supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2＋ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2＋ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.

Preparation and Structural Analysis of Lanthanide Complexes with α-Hydroxyl-phenyl-acetic Acid and 1,10-Phenanthroline as Ligands

A series of ternary lanthanide complexes Ln （C6H5CHOHCOO）3（phen） （H2O） （Ln= La, Ce, Pr, Nd, Sm, Eu） were synthesized with α-hydroxyl-phenyl-acetic acid and 1, 10-phenanthroline （phen） as ligands. The sturcture and property of complexes were characterized by elemental analysis, IR, 1^H-NMR, UV and TGA, and the coordinate mede of both ligands was discussed. It was shown that the co-ordinate mode of 1, 10-phenanthroline was chelated, while α-hydraxyl-phenyl-acetate ion was monedentate or bridging. The mechanism of thermal determinde by thermogravimetry was indicated that the degree of co-ordinate ability of ligand was： α-hydroxyl-phenyl-acetate ion 〉 1, 10- phenanthroline（phen）.

Shift in pKa of 1,10-Phenanthroline in TBAB and PEG-400 Micellar Media: A Potentiometric Study

The acid-base equilibrium of 1,10-phenanthroline (1,10-phen) in the presence of polyethylene glycol 400 (PEG-400, non-ionic) and tetrabutylammonium bromide (TBAB, ionic) micellar media has been studied by Calvin-Wilson titration technique at different mole fractions (0.5% - 2.5%) of PEG-400 and TBAB micellar solutions at an ionic strength of 0.16 mol dm-3 NaCl and at a temperature of 298 K. The pH metric data were subjected to SCPHD program to obtain correction factor and Kw which were given as initial inputs for MINIQUAD75 program to refine protonation constants. HySS program was then used to generate the species distribution diagrams versus pH using the results obtained from the MINIQUAD75 program and SIM run data. The difference in values of protonation constants in aqueous medium (logβ1 = 4.93 & logβ2 = 6.22) and in the micellar media (PEG-400, logβ1 = 4.89 & logβ2 = 5.91 and TBAB, logβ1 = 4.84 & logβ2 = 5.73) is attributed to different intrinsic solvent characteristics of micelles. In case of ionic surfactants, the electrostatic micellar surface is an additional contributing factor.

Synthesis of 5-Substituted 2, 9-Dimethyl-1,10-Phenanthroline Dialdehydes and Their Schiff Bases with Sulfur-Containing Amines

Eight new Schiff bases of 5-nitro and 5-bromo-substituted 1,10-phenanthroline-2,9-dicarboxaldehydes with sulfur-containing amines, thiosemicarbazide, S-alkyl/aryl dithiocarbazates and 2-mercaptoaniline have been synthesized and characterized by a variety of spectroscopic methods. The condensation reactions of the dialdehydes with the amines were carried out both in the presence and absence of conc. sulfuric acid. A significant increase in yield of the Schiff bases was observed when the reactions were carried out in the presence of sulfuric acid.

Antibacterial Activities of New Schiff Bases and Intermediate Silyl Compounds Synthesized from 5-Substituted-1,10-phenanthroline- 2,9-dialdehyde

Schiff bases are known to possess anticancer, antibacterial, antifungal, antitubercular, anti-inflammatory, antimicrobial and antimalarial properties. In this paper antibacterial studies against variety of plants and human pathogenic bacteria with eight newly synthesized Schiff bases and several intermediate silyl compounds have been reported. The antibacterial activities of the synthesized compounds were primarily determined by paper disc diffusion method. The minimum inhibitory concentration (MIC) of each compound was also determined by tube dilution process. Seven different human pathogenic bacteria and eighteen different plant pathogenic bacteria were used for the antibacterial activity studies. While all synthesized compounds have shown significant antibacterial activity, one intermediate silyl compound has shown remarkably high antibacterial property. 5-substituted derivatives have shown relatively higher activity than non-substituted compounds. Polar substituent which increases hydrophilicity may have a positive impact on the antibacterial property.

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)_(2)(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H_(2)DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^(o),V=4056.6(16)A^(3),Z=4,C_(45)H_(22)Cl_(2)F_(2)Mn N_(10)O_(7),M_(r)=978.57,D_(c)=1.602 g/cm^(3),F(000)=1980,μ(Mo Ka)=0.536 mm^(–1),R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^(o),V=4742.0(12)A^(3),Z=8,C_(27)H_(14)Cl Co FN_(4)O_(4),M_r=517.80,D_(c)=1.602 g/cm^(3),F(000)=2312,μ(Mo Ka)=0.889 mm^(–1),R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.

Third-order optical nonlinearities for lanthanum (Ⅲ) complexes with 1,10-phenanthroline components

The nonlinear refractive indexes n 2 for the ethanol solutions of 1,10-phenanthroline (2.0×10 -3 mol·L -1), [bis(1,10-phenanthroline) lanthanum (Ⅲ)] nitrate (1.0×10 -3 mol·L -1), and [nitrato-fluoracil-bis (1,10-phenanthroline) lanthanum (Ⅲ)] nitrate (1.0×10 -3 mol·L -1) are first measured, the third-order nonlinear optical susceptibilities χ (3) and <γ> are calculated, and the mechanisms of the third-order optical nonlinearities enhanced by lanthanum (Ⅲ) are discussed preliminarily.

Distribution mechanism of protonated 1,10-phenanthroline between unbuffered aqueous and 1,2-dichloroethane phases

The faradaic ion transfer of protonated 1,10-phenanthrolino [H(Phen)^+] across the interface between unbuffered aqueous and 1,2-dichloroethane(DCE)solutions was inves- tigated by means of current scan polarography at ascending aqueous electrolyte electrode, as well as chronopotentiometry.It follows from the splitting of the waves observed at the pH of aqueous phase(sodium sulfate solution)between 2.5—3.8 that neutral reagent(Phen) distributes into the aqueous phase,where it is protonated.The positive wave is associated with the mass transfer controlled by the H^+ influx,whereas the negative one is by the Phen influx.The reverse chronopotentiometry indicated that all the protonated transfer processes were reversible.A good agreement between experimental results and theoretical treatment was achieved.The aqueous acid dissociation constant of protonated Phen,K_a,can be evalu- ated from the dependence of the wave heights on the pH in the base of the equilibrium.

Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et_2dtc)_3(phen)

A ternary solid complex Yb（Et2dtc）3（phen） was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate （NaEt2dtc）, and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol. The bonding characteristics of the complex were characterized by IR. The result shows Yb3^＋ bands with two sulfur atoms in the Na（Et2dtc）3 and two nitrogen atoms in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex △rHm^θ（Ⅰ）, was determined as being （-24.838±0.114） kJ·mol^-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex △rHm^θ（s）, was calculated as being （108.015±0.479） kJ·mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction. Fundamental parameters, the activation enthalpy, △H≠^θ, the activation entropy, △S≠^θ, the activation free energy,△G≠^θ, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic expenments. At the same time, the molar heat capacity of the complex cm. p, Was determined to be （86.34± 1.74） J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combus- tion energy of the complex, △cU, was determined to be （ - 17954.08 ± 8.11） kJ·mol^-1 by an RBC-Ⅱ type rotating-bomb calo- rimeter at 298.15 K. Its standard enthalpy of combustion, △cHm^θ, and standard enthalpy of formation, △fHm^θ, were calculated to be （- 17973.29±8.11） kJ·mol^-1 and （-770.36±9.02） kJ·mol^-1, respectively.

Synthesis, Crystal Structure and Fluorescent Properties of a New One-Dimensional Polymer [Sm(sal)_4(phen)_2Na]_n

The title complex, [Sm(sal)_4(phen)_2Na]_n (Ⅰ), where Hsal=salicylic acid, phen=1, 10-phenanthroline, was synthesized by the reaction of samarium chloride with phen and Hsal in ethanol solution and its crystal structure was determined by X-ray diffraction. The crystal is monoclinic, space group C2/c with cell dimensions of a=2 84989 (7) nm, b=0 93347 (2) nm, c=2.27954 (5) nm, β=132.4010 (8)°, V=4.4781 (2) nm^3, Z=4, μ (Mo Kα)=13.97 cm^(-1), D_c=1.605 g·cm^(-3). The title complex is a compound, with centre of the Sm and Na atoms which are bridged by two carboxylate ligands. The structure of the complex demonstrates one-dimensional chain bridged by carboxyl groups. The fluorescence spectrum of the complex indicates that the second ligand phen shows enhancement effect on the fluorescence of the complex.

Synthesis and Structural Characterization of [Mn(phen)_2(H_2O)_2](OAc)_26H_2O

The title complex [Mn(phen)2(H2O)2](OAc)26H2O (phen = 1,10-phenanthroline, C12H8N2, OAc = acetate, C2H3O2) with formula C28H38MnN4O12 and Mr = 677.56 has been syn- thesized and structurally characterized by X-ray diffraction. The crystal is of triclinic, space group P ?with a = 9.6201(5), b = 13.4663(7), c = 14.5375(8) , a = 108.428(1), b =93.898(1), g = 110.492(1), V = 1639.5(2) ?, Dc = 1.373 g/cm3, F(000) = 710, = 0.468 cm-1 and Z = 2. The final refinement gave R = 0.0522 and wR = 0.1259 for 4714 observed reflections with I > 2s(I). It consists of discrete [Mn(phen)2(H2O)2]2+ cation, two acetate anions and six lattice water molecules. The MnII ion coordinated by four nitrogen atoms from two chelating phen and two oxygen atoms from two cis-related water molecules is in a distorted octahedral coordination environment. Two OAc- anions and six water molecules exist outside the [Mn(phen)2(H2O)2]2+ cation as counter ions and solvate molecules, respectively. The cations and anions are interconnected by the solvate water molecules which are hydrogen bonded to both aqua ligands and acetate oxygen atoms, building up the crystals of this compound to be a supramolecule-like aggregate.

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...

A Novel Hybrid Solid Constructed from Tetramolybdate and Copper Complexes with Mixed Ligands: [{(Cu·phen)_2(tp)}{(Cu·phen·H_2O)_2(tp)}{Mo_4O_(14)}]

A novel copper molybdate with mixed ligands, [{（Cu·phen）e（tp）} {（Cu·phen·H2O）2（tp）} {Mo4O14}（phen = 1,10-phcnanthroline, tp = tercphthalate） 1, has been hydrothermally synthesized and structurally characterized. The crystal belongs to monoclinic system, space group P2l/c with a = 13.1711（7）, b = 19.6132（10）, c= 13.6910（7） A, β = 117.6870（10）°, V= 3131.8（3） A^3, Z= 2, C64H44Cu4MoaN8O24, Mr= 1946.99, D, = 2.065 g/cm^3, F（000） = 1920,μ（MoKa） = 2.198 mm ^1, R = 0.0810 and wR = 0.2012 for 4233 observed reflections （I 〉 2σ（I））. The structural analysis indicates that the title compound contains a discrete tetramolybdate cluster decorated with copper colnplcx fragments and tp ligands bridging the clusters into a wave-like layer. The hydrogen bonding between adjacent layers further extends the COlnpound into a 3-D framework.

Thermochemical properties of Ternary Complex Yb[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

A novel ternary solid complex, Yb （C5H8NS2）3 （C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin- edithiocarbamate （ APDC ） and 1, 10-phenanthroline （o-phen· H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous ytterbium chloride, APDC, o-phen·H2O, the mixture of APDC with o-phen· H2O in absolute ethanol at 298. 15 K, and the enthalpy changes of liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^θ）, the apparent reaction rate constant （k）, the apparent activation energy （ E ）, the pre-exponential constant （A） and the reaction order （n）, were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments. The enthalpy change of complex formation from the reaction of the regents in solid phase, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.

Synthesis，Characterization，Crystal Structure and Quantum Chemistry Calculation of the Mixed Ligand Complexes ［Ln（CF_3COO）_3·（Phen）_2·（H_2O）_2］·CH_3COCH_3·H_2O

The complexes of rare earth trifluoroacetate with two 1, 10-phenanthroline Ln (CF_3COO)_3 ·(Phen )_2· CH_3COCH_3·3H_2O (Ln=La, Pr, Nd, Sm, Eu) have prepared in the mixed slovents of H_2O and CH_3COCH_3, and the single crystal Nd (CF_3COO)_3· (Phen )_2· CH_3COCH_3· 3H_2O was determined by four-circle X-ray diffractometer. The crystal is a monoclinic system with space group P2_1/n(14# ), a=0. 9253 ( 1 )nm , b=2. 1500 ( 2 ) nm , c=1.8981 ( 4 ) nm, β= 95. 28( 1 )°, V=3.760(8) nm￣3 , Z=4 , R=0. 035. The coordination number of Nd is 9 , and the coordination polyhedron of Nd atom is distorted tricapped triagonal prism. The electronic structures and chemical bonds of the complex Nd (CF_3COO)_3· (Phen )_2· CH_3COCH_3·3H_2O is studied by the spin unrestricted INDO method.

CuI-catalyzed Synthesis of Aryl Thiocyanates from Aryl Iodides

An operationally simple and inexpensive catalyst system was developed for the cross coupling of potassium thiocyanate with aryl iodides by using CuI as catalyst, 1, 10-phenanthroline as ligand, and tetraethylammonium iodide as activator. The procedure is applicable for the synthesis of diverse aryl thiocyanates without any exotic, poisonous reagents.

A new and convenient synthesis of phendiones oxidated by KBrO_3/H_2SO_4 at room temperature

A new method is described to synthesize phendione derivatives from 1,10-phenanthrolines using potassium bromate and 60% sulfuric acid as oxidant,which was easily applicable to scale-up.The reaction conditions are mild and the yields are excellent.The target compounds have been characterized by 1H NMR,and IR.

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescence of a Novel Two-dimensional Cd(Ⅱ) Coordination Polymer

A new coordination polymer, [Cd2（bptc）（L）2（H2O）2]·5H2O（1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-f][1,10]phenanthroline and H4 bptc = 3,3＇,4,4＇-biphenyltetracarboxylic acid）, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 18.868（4）, b = 7.2111（14）, c = 19.464（4）A, β = 95.75（3）°, C54H31Cd2Cl2F2N8O15, Mr = 1365.57, V = 2635.0（9）A3, Z = 2, Dc = 1.721 g/cm^3, S = 1.034, μ（MoKα） = 0.995 mm^–1, F（000） = 1358, R = 0.0501 and wR = 0.1076. In 1, each bptc anion bridges four Cd（II） atoms to form 2D layer structures, which are further extended by π-π stacking interactions into a 3D supramolecular architecture. The thermal behavior and luminescent properties of the compound have also been studied.

Investigation of Ru(phen)_3^(2+)-Hydrazine-Ce(Ⅳ) Chemiluminescence System and Its Analytical Application

It was observed that hydrazine could enhance the chemiluminescence （CL） intensity of tris-（1,10 phenanthroline）ruthenium（Ⅱ） （Ru（ phen）3^2＋ ）- Cerium（ Ⅳ ） ice（ Ⅳ ）） system, based on which, a novel CL system, Ru（phen）3^2＋ Hydrazine-Ce（Ⅳ）, was established. This CL system was investigated and employed to detect hydrazine. Under the optimum experimental conditions, the linear range and detection limit of the proposed method are 2.0× 10^-6-2.0×10^-3g·L^-1 and 1. 8×10^-6g·L^-1, respectively. For 1. 5 × 10^-5, 1.5×10^-4 and 1.2×10^-3 g·L^-1 hydrazine, the relative standard deviation （RSD） is 2.9%, 2.2% and 3. 1%, respectively （n= 11）. The proposed method has been used to detect the content of hydrazine in the synthetic samples with satisfactory results.