Mixed Azide and 5-(Pyrimidyl)tetrazole Bridged Co(II)/Mn(II) Polymers: Synthesis, Crystal Structures, Ferroelectric and Magnetic Behavior

The reaction of pyrimidine-2-carbonitrile, NaN3 in the presence of Co(NO3)(2)center dot 6H(2)O or MnCl2 center dot 4H(2)O leads to the formation of complexes Co(pmtz)(mu(1,3)-N-3)(H2O)](n) (1) and Mn(pmtz)(mu(1,3)-N-3)(H2O)](n) (2) respectively, under hydrothermal condition pmtz =5-(pyrimidyl)tetrazolate]. These two complexes have been fully characterized by single crystal X-ray diffraction. Complex 1 crystallizes in a non-centrosymmetric space group Aba2 in the orthorhombic system and is found to exhibit ferroelectric behavior, whereas complex 2 crystallizes in the P2(1)/c space group in the monoclinic system. Variable temperature magnetic characterizations in the temperature range of 2-300 K indicate that complex 1 is a canted antiferromagnet (weak ferromagnet) with T-c = 15.9 K. Complex 1 represents a unique example of a multiferroic coordination polymer containing tetrazole as a co-ligand. Complex 2 is a one-dimensional chain of Mn(II) bridged by a well-known antiferromagnetic coupler end-to-end azido ligand. In contrast to the role played by the end-to-end azido pathway in most of the transition metal complexes, complex 2 showed unusual ferromagnetic behavior below 40 K because of spin canting.

Macrocycle-Terminated Core-Cross-Linked Star Polymers: Synthesis and Characterization

We have synthesized macrocyclic polystyrene- (PS-) terminated PS star polymers via a core-cross-linking approach in this work. A tadpole-shaped macrocyclic PS-linear-PS copolymer was synthesized at first via click chemistry and ATRP polymerization method. The "living" ATRP initiating chain-ends of the tadpole-shaped copolymers were linked together via ATRP polymerization with divinylbenzene to form a core-cross-linked macrocyclic star polymer. The number of arms attached to the macrocyclic star polymers was measured with NMR. and absolute molecular weights with gel permeation chromatography (GPC) with multiangle laser light scattering detector. These macrocyclic star polymers had a highly cross-linked core and many radiating arms. The shorter tadpole-shaped precursors caused core-cross-linked star polymers with higher molecular weights and more arm numbers. The macrocycle-terminated core-cross-linked star polymers showed two glass transition temperatures, one arising from the linear branches and another from the macrocycles.

Development of Photorefractive Polymers: Synthesis and Characterization of Polymers with Donor-Pi-Acceptor Groups

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Novel Approaches to Biodegradable Polymers: Synthesis and Biodegradation Studies

Biodegradable polymers have opened an emerging area of great interest because they are the ultimate solution for the disposal problems of synthetic polymers used for short time applications in the environmental and biomedical field. The biodegradable polymers available until recently have a number of limitations in terms of strength and dimensional stability. Most of them have processing problems and are also very expensive. Recent developments in biodegradable polymers show that monomers and polymers obtained from renewable resources are important owing to their inherent biodegradability, biocompatibility and easy availability. The present study is, therefore, mostly concemed with the utilization of renewable resources by effecting chemical modification/copolymerization on existing synthetic polymers/natural polymers for introducing better biodegradability and material properties.The thesis describes multiple approaches in the design of new biodegradable polymers: (1) Chemical modification of an existing nonbiodegradable polymer, polyethylene, by anchoring monosaccharides after functionalization to introduce biodegradability. (2) Copolymerization of an existing biodegradable polymer, polylactide, with suitable monomers and/or polymers to tailor their properties to suit the emerging requirements such as (2a) graft copolymerization of lactide onto chitosan to get controlled solvation and biodegradability and (2b) copolymerization of polylactide with cycloaliphatic amide segments to improve upon the thermal properties and processability.

Blue, Green and Orange-Red Light Emitting Polymers: Synthesis, Characterization and Prospects of Applications in Optoelectronic Devices

Light emitting polymers (LEPs) are considered as the second generation of conducting polymers. A Prototype LEP device based on electroluminescence emission of poly(p-phenylenevinylene) (PPV) was first assembled in 1990. LEPs have progressed tremendously over the past 20 years. The development of new LEP derivatives are important because polymer light emitting diodes (PLEDs) can be used for the manufacture of next-generation displays and other optoelectronic applications such as lasers, photovoltaic cells and sensors. Under this circumstance, it is important to understand thermal, structural, morphological, electrochemical and photophysical characteristics of luminescent polymers. In this thesis the author synthesizes a series of light emitting polymers that can emit three primary colors (RGB) with high efficiency

Synthesis of Hyperbranched Polymers with Pendent Norbornene Functionalities via RAFT Polymerization of a Novel Asymmetrical Divinyl Monomer

Hyperbranched polymers with numerous pendent norbornene functionalities have been synthesized via the radical polymerization of a novel asymmetrical divinyl monomer hearing a higher reactivity methacrylate group and it lower reactivity norbornene group. Mediated by a rapid reversible addition-fragmentation chain transfer (RAFT) equilibrium, the concentration of polymeric chain radicals is decreased, and thus the gelation did not occur until higher monomer conversions (ca. 90%). An increase in reaction temperature call also significantly promote the formation of the hyperbranched structure owing to the decreased stability of the intermediate radicals derived from the norbornene group, which was confirmed by a model copolymerization system of two single vinyl monomers with similar structures to the vinyl groups in the asymmetrical divinyl monomer. Furthermore, Tri-SEC and conventional Sin-SEC as well as H-1 NMR.

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] (n) center dot 2nH(2)O (1), [Pd(fum)(bpe)] (n) center dot nH(2)O (2) and [Pd(fum)(pz)] (n) center dot 3nH(2)O (3) {bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and (13)C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46-491 A degrees C. In all the cases, metallic palladium was identified as the final residue.

Synthesis and characterization of an active styrlthiophene monomer and its polyurethane with second-order optical nonlinearity

A novel monomer, (trans)-7-[4-N,N-(di-beta-hydroxyethyl) amino-benzene]-ethenyl-3,5-dinitrothiophene (HBDT), and the corresponding prepolymer, polyurethane were synthesized and characterized. The details of synthesis of the monomer and its further polymerization were presented. The prepolymer and polyurethane exhibited good thermal stability and good solubility in common organic solvents. The d(33) coefficient of the poled films was determined to be 40.3 pm/V. (C) 2000 Kluwer Academic Publishers.

Synthesis and Properties of Carbazole Main Chain Copolymers with Oxadiazole Pendant toward Bipolar Polymer Host: Tuning the HOMO/LUMO Level and Triplet Energy

Three new carbazole copolymers, poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-3,6-diyl)s (P1), poly(9-(2,5-diarene-[1,3,4]oxadiazole)-2, 7-carbazole-alt-9-(2-ethylhexyl)-3, 6-carbazole-diyl)s (P2), and poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-2,7-diyl)s (P3), were synthesized by the Suzuki coupling reaction

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Synthesis and property of a novel sulfonated poly(ether ether ketone) with high selectivity for direct methanol fuel cell applications

Bisphenol monomer 4-carboxylphenyl hydroquinone (4C-PH) containing carboxyl groups was synthesized by diazotization reaction of p-aminobenzoic acid and 1,4-benzoquinone and subsequent reductive reaction. Copolymerization of bisphenol A, 4C-PH, sodium 5,5'-carbonylbis(2-fluorobenzene-sulfonate) and 4,4'-difluorobenzophenone at various molar ratios through aromatic nucleophilic substitution reaction resulted in a new sulfonated poly(ether ether ketone) containing pendant carboxyl groups (C-SPEEK). The structures of the monomer 4C-PH and copolymers were confirmed by FT-IR and H-1 NMR. Flexible and transparent membranes with sulfonic and carboxylic acid groups as the proton conducting sites were prepared. The dependence of ion-exchange capacity (IEC), water uptake, proton conductivity and methanol permeability on the degree of sulfonation has been studied.

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

Synthesis of Aromatic Oxide-Oxadiazoles Containing Pyridine Ring and Study on Their Spectral Properties

In order to explore new highly organic electroluminescent materials, six symmetrical aromatic oxide-oxadiazoles containing pyridine ring 4a similar to 4f were synthesized through cyclization of substituted benzoic acid (2) with 2,6-dihydrazide pyridine (3) by "one-pot" method in POCl3. Their structures were confirmed by MS, IR, H-1 NMR techniques and elemental analysis. The fluorescence spectra of the target compounds showed that the A,m ranged from 347 to 507 nm, and the maximum A,m were close to 384 nm, which showed that these compounds have good fluorescence with strong fluorescence intensity. When the 5-Br group was introduced into the aromatic ring (4e and 4f), the fluorescent emission wavelength took place Einstein shift, and the fluorescent intensity decreased a little. Using quinine bisulphate as a reference, the fluorescence quantum yields were all tested, and the introduction of 5-Br group had no visible effect on fluorescence quantum yield.

Synthesis and characterization of rigid-rod sulfonated polyimides bearing sulfobenzoyl side groups as proton exchange membranes

A novel wholly aromatic diamine, 2,2 '-bis(3-sulfobenzoyl)benzidine (2,2 '-BSBB), was successfully prepared by the reaction of 2,2 '-dibenzoylbenzidine (2,2 '-DBB) with fuming sulfuric acid. Copolymerization of 1,4,5,8-naphathlenetetracarboxylic dianhydride with 2,2 '-BSBB and 2,2 '-DBB generated a series of rigid-rod sulfonated polyimides. The synthesized copolymers with the -SO3H group on the side chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendent groups. They displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. The proton conductivities of copolymer membranes increased with increasing IEC and temperature, reaching value above 1.25 x 10(-1) S/cm at 20 degrees C, which is higher than that of Nafion (R) 117 at the same measurement condition. They displayed reasonably high proton conductivity due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water to occupy, taking their lower water uptake (WU) into account. Consequently, these materials proved to be promising as proton exchange membrane.