Physicochemical and Analytical Studies of Some Monomer and Polymer Complexes Derived from Selected Aroyl Hydrazone

New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co2+, Ni2+, and Cu2+ salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co2+ and Fe3+ ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co2+ ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni2+ and Cu2+. Finally, conductance titration of HNB and HNT with Co2+ ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co2+-HNB while 1:1 (M:L) belongs to the Co2+-HNT system.

Alcohol-dispersed polymer complex as an effective and durable interface modifier for n-i-p perovskite solar cells

Abundant interfacial defects remain a significant challenge that hampers both the efficiency and stability of perovskite solar cells(PSCs).Herein,an alcohol-dispersed conducting polymer complex,denoted as PEDOT:F(Poly(3,4-ethylene dioxythiophene):Perfluorinated sulfonic acid ionomers),is introduced into the interface between perovskite and hole transporting layer in regular-structured PSCs.PEDOT:F serves as a multi-functional interface layer(filling grain boundaries and covering perovskite's grain-surface)to achieve a robust interaction with organic groups within perovskites,which could induce a structural transformation of PEDOT to increase its conductivity for the efficient hole-transport.Furthermore,the strong interaction between PEDOT and perovskites could promote an effective coupling of undercoordinated Pb~(2+)ions with the lone electron pairs near O&S atoms in PEDOT molecules,thereby enhancing defect passivation.Additionally,PEDOT:F with inherent hydrophobic properties prevents effectively moisture invasion into perovskites for the improved long-term stability of the PSCs.Consequently,the PEDOT:F-based PSCs achieved a champion efficiency of 24.81%,and maintained ca.92%of their initial efficiency after 7680 h of storage in a dry air environment,accompanied by the enhanced photothermal stability.

Electrospinning of supramolecular polymer complexes

Supramolecular polymer complexes with small molecules are self-assembled through non-covalent interactions and have been proposed for a wide variety of applications in materials science and nanoscience.Our research group has recently shown the possibility of forming highly ordered nanofibers of supramolecular complexes in their thermodynamically stable state using the electrospinning technique.The ultrafast solvent evaporation rate of electrospinning made possible the in-depth characterization of complexes that had never been prepared in their pure state before because of kinetic issues associated with their formation by conventional approaches.The improved understanding of the formation mechanism allowed us to extend the concept to other techniques featuring a fast solvent evaporation rate,such as electrospray and spin-coating.In this article,we review our most significant contributions in this research field.

Synthesis and Photophysical Properties of Dy^(3+) and Gd^(3+) Polymeric Complexes with Functionalized Polybenzimidazole Containing β-Diketone Side Group

The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.

PREPARATION AND MAGNETIC PROPERTIES OF POLYMERIC COMPLEXES CONTAINING 1,10-PHENANTHROLINE

A series of polymeric complexes were prepared from Fe^2＋, Co^2＋ or Ni^2＋ and poly（Schiff base） （DAPcIPA）, which was obtained by polycondensation of 5,6-diamino-1,10-phenanthroline （DAP） with isophthalaldehyde （IPA）. The structures of the polymer and the polymeric complexes were characterized by IR, 1^H-NMR and elemental analysis. The magnetic behavior of these complexes was measured as a function of magnetic field strength （0-3.98 ~ 106 A/m） at 5 K and as a function of temperature （5-300 K） at a magnetic field strength of 2.39 × 10^6 A/re. Experimental results show that DAPcIPA-Ni^2＋, DAPcIPA-Co^2＋ are soft ferromagnets while DAPcIPA-Fe^2＋ exhibits features of an antiferromagnet.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

Comparative Studies of Some Novel Cu(II) Polymeric Complexes Derived from Cyanoacetylhydrazine (CAH;L). The Role of Solvents Used on the Structure and Geometry of the Isolated Cu²⁺Complexes

Novel polymeric Cu2+ complexes derived from the reaction of cyanoacetylhydrazine (CAH;L) with CuCl2•2H2O in different solvents were synthesized and characterized. The isolated solid polymeric complexes were investigated using modern conventional physicochemical and spectral (IR, 1H-NMR, UV-Vis. ESR, Raman), magnetic and thermal studies. The results revealed that CAH behaves in different ways towards the coordination of the Cu2+ ion. The promotion of solvents to the cyano group was discussed on the basis of the solvent and the Cu2+ ion used. Magnetic and spectral studies suggest octahedral geometry is proposed for the Cu2+ complexes. EPR studies indicate the existence of polymeric complexes depending on the results of g-values. The results suggest that the number of copper atoms ranges from three to twelve atoms. The molecular modeling is drawn and some chemical characteristics are calculated such as chemical reactivity and energy components are investigated between the different types of the ligands.

STUDY ON POLYMER-Ru-Co BIMETALLIC COMPLEXES CATALYSTS Ⅱ.X-RAY PHOTOELECTRON SPECTROSCOPIC ANALYSIS

Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co_2_p and Ru_(3d) of XPS peaks are close to each other and both are high,the catalyst exhibits its maximum activity The mechanism ofcatalytic hydroformylation has been discussed.

RARE EARTH CONTAINING POLYMER TERNARY COMPLEXES AND THEIR FLUORESCENT PROPERTIES

Rare earth containing fluorescence active polymer ternary complexes were synthesized and their absorption and emission properties were investigated.

Examination of Polymeric Azomethine Compounds and Their Transition Metal Complexes by Using XRF and XRD Technique

In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.

STUDIES ON ORGANO-MOLYBDENUM AND TUNGSTEN COMPOUNDS(Ⅲ)——CATALYTIC POLYMERIZATION OF ACETYLENE BY M-O-C BOND-CONTAINING COMPLEXES OF Mo AND W

Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined.

Synthesis and characterization of yttrium-aluminum-iron and yttrium-cerium-iron citric complexes

Fe-, Y-Fe-Al- and Y-Ce-Fe- citrates were synthesized in ethylene glycol （EG） medium under conditions similar to those used in the polymerized complex method. Their elemental composition, IR,^ 13C and ^1H NMR, X-ray photoelectron and Mossbauer spectra were studied, and formulae describing their composition were proposed. The complexes contained EG bonded as adduct and ester with citric acid ligand and did not contain ligands with deprotonated alcoholic groups. The complexes consisted of agglomerated spheres, 0.7-3 μm in diameter. The local composition of the products was established by energy dispersive X-ray microanalysis. The comparison of the number of the ligands, their average electrical charge and the esterification degree of mono-, di- and trimetallic complexes proved the mixed-metal nature of the species studied. The thermal decomposition of the complexes was studied and a general scheme of the processes taking place was proposed. Highly crystalline, phase homogeneous YaFe4AlO12 was produced after heating the respective complex at 1000 ℃. Ce-doped yttrium-iron garnet, similarly prepared, contained traces of CeO2.

Polymeric complex micelle loaded with axially substituted silicon(Ⅳ) phthalocyanine

A novel axially substituted silicon（IV） phthalocyanine, namely di-pyridyloxy axially substituted silicon（IV） phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^e-（benzyloxycarbonyl-lysine]-poly（ethylene glycol）-poly [N^e-（benzyl oxycarbonyl） （PLL（Z）-b-PEG-b-PLL（Z）） to form hydrophobic 2-loaded polymeric complex micelle （PIC） （2-loaded P/C）. Atom force microscopy （AFM） image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced bv the incorporation 2 into PIC nanocarrier.

Measurement Method of the Thickness Uniformity for Polymer Films

Several methods for investigating the thickness uniformity of polymer thin films are presented as well as their measurement principles. A comparison of these experimental methods is given.The cylindrical lightwave reflection method is found to can obtain the thickness distribution along a certain direction.It is a simple and suitable method to evaluate the film thickness uniformity.

Polymerization of Phenyl Isocyanate by Divalent Samarium Complex (ArO)_2Sm(THF)_4 (ArO=2,6-di-tert-butyl-4-methylphenoxo)

Phenyl isocyanate was for the first time successfully polymerized by divalent samarium complex (ArO)2Sm(THF)4. The monomer concentration and temperatur affected the polymerization greatly.

Synthesis and Crystal Structure of a Novel Bis(chlorido)-bridged One-dimensional Chain-like Copper(Ⅱ) Polymer

A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387（2）, b = 9.968（2）, c = 10.291（2） ？, α = 87.532（3）, β = 63.762（2）, γ = 86.628（3）o, V = 862.1（3） ？^3, Z = 1, Dc = 1.640 Mg/m^3, F（000） = 428, R = 0.0416 and wR = 0.1141. Each Cu（Ⅱ） metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper（Ⅱ） complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.

A Novel Phenoxyimine-based Schiff Base Ligand and Its Mononuclear Nickel(Ⅱ) Complex：Synthesis,Crystal Structure,Norbornene Polymerization and Catalytic Activity

A novel phenoxyimine-based Schiff base ligand and its mononuclear complex [C（58）H（52）N2NiO2]（L = 2-benzhydryl-4-dimethoxy-3,5-dimethyl-salicylaldehyde） has been synthesized and characterized by IR spectrum, elemental analysis, TG, WAXD spectra, ^1H NMR and ^（13）C NMR. In addition, the molecular structure has been measured by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 14.510（6）, b = 18.573（7）, c = 20.961（6） A, β = 123.453（19）°, V = 4713（3）A^3, Mr = 867.73, Z = 4, Dc = 1.223 g/cm^3, μ = 0.456 mm^-1, F（000） = 1832, the final R = 0.0685 and wR = 0.1758（I 〉 2σ（I））. The complex was used as homogeneous catalysis of polymerization of norbornene, and the MAO as cocatalyst. The nickel complex exhibited good catalytic activity up to 1.913 × 10^7 g of PNB（mol of Ni）^-1h^-1,and the yields of these reactions depend on the nature of the substituent in the aromatic ring.

Synthesis, Structure and Norbornene Polymerization Catalyzed by Nickel(Ⅱ) Complex Bearing N,O-bis(1-(6-ethylpyridin-2-ylimino)-methylenyl)naphthalen-2-ol Ligand

The title complex bis{1-{[（6-ethyl-2-pyridinyl）imino]methylenyl}-2-naphthale- nolato-N,O}-nickel（lI） （C36H32NnO2Ni） has been synthesized by the reaction of l-{[（6-ethyl-2- pyridinyl）imino]methylenyl}-2-naphthalenol with Ni（CH3COO）2·4H2O, and characterized by IR spectrum, elemental analysis and TG. The complicated space structure has been confirmed by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.410（4）, b = 14.382（4）, c = 18.121（6） ,A, β = 97.147（6）% V= 2950.5（16）A3, C36H32N4O2Ni, Mr = 611.37, Z = 4, Dc = 1.376 g/cm3, μ = 0.698 mm-1 F（000） = 1280, the final R = 0.0519 and wR = 0.1493 （1 〉2σ（I））. This title compound was used as precatalysts for the polymerisation of norbornene. When activated with MAO, the complex exhibited excellent catalytic activity up to 1.98 × 107 g ofPNB （mol of Ni）-1 h-1 with high monomer conversion.

Two Cobalt(Ⅱ)Coordination Polymers Based on Tetrazylphosphonate and Tetrazylphosphonic Acid Ligands

Two cobalt coordination polymers with the same 2D structure have been hydrothermally synthesized based on two bifunctional ligands with tetrazole and phosphonate（phosphonic acid） groups,namely,diethyl 4-（2H-1,2,3,4-tetrazol-5-yl） benzylphosphonate（C_2H_5-L1） and 4-（2H-1,2,3,4-tetrazol-5-yl）benzylphosphonic acid（H_2L2）. The structures of the two complexes are characterized by elemental analysis,IR,TGA and X-ray single-crystal/powder diffraction. The pink block crystals of complex [Co（L1）（H_2O）]·H_2O（1） belong to the monoclinic system,space group C2/m with a = 20.8390（11）,b = 7.2695（3）,c = 10.0156（6） A,β = 109.773（7）°,V = 1427.80（13） A^3,Z = 4,D_c = 1.680 mg/cm^-3,M_r = 361.16,F（000） = 740,R = 0.0316 and wR = 0.0826 for 1702 observed reflections（I 〉 2σ（I））. The purple block crystals of complex [Co（L2）（H_2O）]·2H_2O（2） also belong to the monoclinic system,space group C2/c with a = 25.5382（16）,b = 7.3844（3）,c = 15.1925（11） A,β = 124.238（9）°,V = 2368.6（2） A^3,Z = 8,D_c = 1.969 mg/cm^-3,M_r = 351.12,F（000） = 1432,R = 0.0475,wR = 0.1617 for 2088 observed reflections（I 〉 2σ（I））. Both the nitrogen atoms of tetrazole group and oxygen atoms of phosphonate（phosphonic acid） groups in the ligands coordinated with the metal cobalt. The magnetic property of complex 1 is also investigated.

Synthesis and Magnetic Properties of Fe（Ⅱ） and Nd（Ⅲ） Complexes of Poly（N-2-thiazolylacrylamide）

N-2-Thiazolylacrylamide （NTA） was polymerized by a radical route to obtain the polymer in good yield. The polymer with a pendent heterocyclic group is soluble in common organic solvents, which allow to prepare the corresponding metal complexes with higher loads easily. FTIR, ^1H NMR, elemental analysis, and energy-dispersive X-Ray spectroscopy （EDX） were applied to characterize these materials. The magnetic behavior of Fe（Ⅱ） and Nd（Ⅲ） complexes of poly（N-2-thiazolylacrylamide） was examined by a PPMS-9T magnetometer, exhibiting the characteristics of a soft ferromagnet. It is found that the Nd（Ⅲ） complex has an extremely high relative saturation magnetization of 35 emu/g.