Simultaneous novel synthesis of conducting and non-conducting halogenated polymers by electroinitiation of (2,4,6-trichloro- or 2,6-dichlorophenolato)Ni(II) complexes

Ozalp-Yaman, S
Basturkmen, M
Kisakurek, D
NiL2(Ph)(2)(.)xH(2)O [L=3,5-dimethylpyrazole or N-methyl imidazole; Ph=DCP or TCP; x=0, 1 or 3] complexes were synthesised and characterised by analytical and spectroscopic methods using elemental analysis and FTIR. The electrochemical behavior of the complexes was studied by cyclic voltammetry in tetrabutylammoniumtetrafluoroborate-N,N-dimethylformamide electrolyte-sol vent couple. Cyclic voltammogram of the complexes displayed two-step oxidation processes under the nitrogen gas atmosphere. The polymerization of the complexes was accomplished in the same solvent-electrolyte couple by the constant potential electrolysis of NiL2(Ph)(2)(.)xH(2)O, synthesizing the poly(di- or monochlorophenylene oxide)s via free radical mechanism. The simultaneous polymerization of non-conducting polymer and conducting polymer (the conductivity of 0.7 S cm(-2)) were achieved by electroinitiated polymerization of Ni(DMPz)(2)(TCP)(2). The structural analysis of the polymers were performed using FTIR, H-1 NMR and C-13 NMR spectroscopic techniques and DSC for the thermal analysis. The kinetics of the polymerization was followed by in situ UV-vis spectrophotometer during the electrolysis. The low temperature ESR spectrum of the electrolysis solution also confirmed the formation of phenol radical (g=2.0028). One electron oxidation process of NiL2(DCP)(2)(.)xH(2)O produces a new Ni(II) complex, Ni(L-L)(DCP)(2)(S) by the rapid decomposition of (NiL2)-L-III(DCP)(2) into a ligand radical producing a singlet with the g value of 2.0015. Second electron oxidation process generates oligemers, which could not be isolated from the electrolyte solution.


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A new monomer, octa(thiophenephenyl)silsesquioxane (OThiophenePS) was synthesized via click chemistry. The chemical structure of OThiophenePS was characterized by nuclear magnetic resonance (H-1 NMR) and Fourier transform infrared (FT-IR) spectroscopies. Electrochemical polymerization of pyrrole with OThiophenePS was performed resulting in polypyrrole-attached, polyhedral oligomeric silsesquioxane (OPS-PPy). The spectroelectrochemical studies show that the electrochromic properties of (OPS-PPy) are superior...
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Poly(4-vinylpyridine)-b-Poly(dimethylsiloxane) (P4VP-b-PDMS) copolymers have been synthesized by sequential anionic polymerization of 4VP and hexamethylcyclotrisiloxane at - 70-degrees-C. The initiator was sodium naphthenate. The solvent used during reactions has a very critical role in an homogeneous polymerization medium. A 1:1 pyridine/THF mixture was found to be the most suitable. The products were characterized by H-1-NMR spectroscopy, transmission electron microscopy (TEM) and differential scanning ca...
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Electroinitiated copolymerization of indene with β-methoxystyrene was carried out at 0°C and five different potentials. Monomer consumption was studied by cyclic voltammetry. It is known that, when the difference between oxidation potentials of two monomers is large, polymerization potential affects copolymer composition. In the present study indene and β-methoxystyrene were selected because their oxidation potentials are almost equal, ca. + 1.40 V. The effect of polymerization potential on copolymer compos...
Highly efficient polymer blends from a polyfluorene derivative and PVK for LEDs
NOWACKI, Bruno; IAMAZAKI, Eduardo; Çırpan, Ali; KARASZ, Frank; ATVARS, Teresa D.Z.; AKCELRUD, Leni (Elsevier BV, 2009-11-27)
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Citation Formats
S. Ozalp-Yaman, M. Basturkmen, and D. Kisakurek, “Simultaneous novel synthesis of conducting and non-conducting halogenated polymers by electroinitiation of (2,4,6-trichloro- or 2,6-dichlorophenolato)Ni(II) complexes,” POLYMER, pp. 6786–6796, 2005, Accessed: 00, 2020. [Online]. Available: