Faculty Publications
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Item Synthesis and characterization of new light-emitting copolymers containing 3,4-dialkoxythiophenes(2006) Udayakumar, D.; Vasudeva Adhikari, A.V.We report the synthesis, optical and electrochemical properties of a new series of polyoxadiazoles (P1-P3) consisting of 3,4-dialkoxythiophene and 1,4-divinylbenzene units. The polymers are prepared using the precursor polyhydrazide route. The polymers have well defined structure and exhibit good thermal stability with the onset decomposition temperature in nitrogen at around 330 °C. The optical and charge-transporting properties of the polymers are investigated by UV-vis spectroscopy, fluorescence emission spectroscopy and cyclic voltammetry. The UV-vis absorption spectra of polymers in solution showed a maximum at around 380 nm. The polymers depicted bluish-green fluorescence in solutions and green fluorescence in thin films. Cyclic voltammetry studies reveal that these copolymers have low-lying LUMO energy levels ranging from 3.25 to 3.31 eV and HOMO energy levels ranging from 5.48 to 5.56 eV, which indicated that the polymers are expected to provide enhanced charge-transporting (electron transport/hole blocking) properties for the development of efficient polymer light-emitting diodes (PLEDs). © 2006 Elsevier B.V. All rights reserved.Item Synthesis and characterization of fluorescent poly(oxadiazole)s containing 3,4-dialkoxythiophenes(Elsevier, 2007) Udayakumar, D.; Vasudeva Adhikari, A.V.We report the synthesis, optical and electrochemical details, and properties of three conjugated copolymers (P1-P3) consisting of alternate hole-transporting thiophene derivative and electron-transporting 1,3,4-oxadiazole units. The polymers are prepared using the precursor polyhydrazide route. The polymers have well defined structure and exhibit good thermal stability with the onset decomposition temperature in nitrogen at around 300 °C. All the polymers are soluble in organic solvents such as DMF, DMSO, NMP and in strong organic acids like trifluoroacetic acid. The optical and charge-transporting properties of the polymers are investigated by UV-visible spectroscopy, fluorescence emission spectroscopy and cyclic voltammetry. The UV-visible absorption spectra of polymers in solution showed a maximum at around 400 nm. The polymers depicted green fluorescence both in solution and as thin films. Cyclic voltammetry studies reveal that these copolymers have low-lying LUMO energy levels ranging from -3.28 to -3.36 eV and high-lying HOMO energy levels ranging from -5.5 to -5.56 eV, which indicated that they may be promising candidates for electron-transporting or hole-blocking materials in light-emitting diodes. © 2006 Elsevier B.V. All rights reserved.Item Synthesis and characterization of novel conjugated copolymers containing 3,4-dialkoxythiophene and 1,3,4-oxadiazole units(2007) Udayakumar, D.; Vasudeva Adhikari, A.V.In this report we describe the synthesis, optical and electrochemical properties of new conjugated copolymers (P1-P4) based on 3,4-dialkoxythiophene and 1,3,4-oxadiazole units. The copolymers are prepared using the precursor polyhydrazide route. The chemical structures of the copolymers are confirmed using FTIR, NMR spectroscopy and CHNS analysis. The polymers exhibit good thermal stability with the onset decomposition temperature in nitrogen at around 300 °C. The optical and charge-transporting properties of the copolymers are investigated by UV-visible absorption spectroscopy, fluorescence emission spectroscopy and cyclic voltammetry. The polymers depicted blue/green fluorescence under the irradiation of UV light. Cyclic voltammetry studies reveal that these copolymers have low-lying LUMO energy levels ranging from -3.28 to -3.32 eV and high-lying HOMO energy levels ranging from -5.26 to -5.62 eV, which indicated that they may be promising candidates for the fabrication of polymer light-emitting diodes. In addition, the copolymers showed good third-order non-linear optical properties. © 2007 Elsevier Ltd. All rights reserved.Item Synthesis and nonlinear optical characterization of copolymers containing alternating 3,4-dialkoxythiophene and 1,3,4-oxadiazolydbenzene units(2007) Udayakumar, D.; Kiran, A.J.; Vasudeva Adhikari, A.V.; Chandrasekharan, K.; Shashikala, H.D.We report the synthesis and linear and third-order nonlinear optical (NLP) characterization of two novel copolymers containing alternating 3,4-dialkoxythiophene and 1,4-bis(1,3,4-oxadiazolyl)benzene units. The copolymers were synthesized with a precursor polyhydrazide route. Both copolymers exhibited fluorescence around 430 nm under the irradiation of UV light. The NLO measurements were made with the single-beam Z-scan technique with Nd:YAG nanosecond laser pulses at 532 nm. The nonlinear refractive index of the investigated copolymers was negative, and the magnitude was as high as 10 -10 esu. The samples exhibited strong reverse saturation absorption and very good optical limiting properties at the wavelength used. The concentration dependence of third-order NLO parameters was studied. ©2007 Wiley Periodicals, Inc.Item Third-order nonlinear optical susceptibilities of new copolymers containing alternate 3,4-dialkoxythiophene and (1,3,4-oxadiazolyl)pyridine moieties(Elsevier, 2009) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.; Poornesh, P.; Umesh, G.A new series of conjugated copolymers (P1-P3) consisting of alternate 3,4-dialkoxythiophene and (1,3,4-oxadiazolyl)pyridine moieties have been synthesized using the precursor polyhydrazide route. They have been characterized by FTIR, 1H NMR spectral and elemental analyses. These copolymers possess well defined structure and exhibit good thermal stability with the onset decomposition temperature in nitrogen at around 300 °C. Their molecular weights were determined by gel permeation chromatography (GPC). The optical and charge-transporting properties of the copolymers were investigated by UV-visible spectroscopy, fluorescence emission spectroscopy and cyclic voltammetry. Their UV-visible absorption spectra showed a ?max at around 342 nm and displayed bluish-green fluorescence in solution state. The band gaps were found to be at about 2.55 eV for all the copolymers. The third-order nonlinear optical properties (NLO) of these copolymers were studied by Z-scan technique. The measurements were performed at 532 nm with 7 ns laser pulses using a Nd:YAG laser in solution form. The real part of ?(3) were estimated to be -0.881 × 10-12, -0.901 × 10-12 and -1.030 × 10-12 esu for P1, P2 and P3 respectively. The imaginary part of ?(3) for the copolymers P1, P2 and P3 were determined to be 0.192 × 10-12, 0.253 × 10-12 and 0.272 × 10-12 esu respectively. The copolymers exhibit strong reverse saturable absorption and good optical limiting behaviour at 532 nm. © 2008 Elsevier B.V. All rights reserved.Item Design and synthesis of new donor-acceptor type conjugated copolymers derived from thiophenes(2009) Manjunatha, M.G.; Vasudeva Adhikari, A.V.; Hegde, P.K.A new series of donor-acceptor type poly(thiophene) derivatives (P1-P3) were synthesized starting from thiodiglycolic acid and diethyl oxalate through multistep reactions. In the final step, the polymerization was carried out using Wittig reaction. This is a good synthetic route for the preparation of any desired p- and n-type copolymers. The optical and potential charge-transporting properties of the copolymers were investigated by UV-vis, fluorescence emission spectroscopy and cyclic voltammetry. The copolymers exhibited bluish-green/green fluorescence in their thin film forms. Cyclic voltammetry experiments showed that these copolymers have low-lying LUMO energy levels ranging from -2.98 to -3.11 eV and high lying HOMO energy levels ranging from -5.45 to -5.65 eV. The optical and electrochemical studies reveal that new copolymers are new promising materials for the development of efficient polymer light emitting diodes. © 2008 Elsevier Ltd. All rights reserved.Item Synthesis and nonlinear optical characterization of new poly{2,2?-(3,4-didodecyloxythiophene-2,5-diyl)bis[5-(2-thienyl)-1,3,4-oxadiazole]}(2009) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.; Suchand Sandeep, C.S.; Philip, R.A new donor-acceptor type poly{2,2?-(3,4-didodecyloxythiophene-2,5-diyl)bis[5-(2-thienyl)-1,3,4-oxadiazole]} (P) was synthesized starting from thiodiglycolic acid and diethyl oxalate through multistep reactions. The polymerization was carried out using chemical polymerization technique. The optical and charge-transporting property of the copolymer was investigated by UV-vis, fluorescence emission spectroscopic and cyclic voltammetric studies. The copolymer shows UV absorption maxima at 375 nm and displays bluish-green fluorescence in DMF solution. Its electrochemical band gap was determined to be 2.07 eV. The nonlinear optical (NLO) properties of the copolymer was investigated at 532 nm using single beam Z-scan and degenerate four-wave mixing (DFWM) techniques with nanosecond laser pulses. The copolymer exhibits strong optical limiting behavior due to effective three-photon absorption (3PA). Values of the effective 3PA coefficient (?), third-order nonlinear susceptibility (?(3)) and figure of merit (F) have been calculated. © 2009 Elsevier B.V. All rights reserved.Item Optical characterization of a new Donor-acceptor type conjugated polymer derived from 3,4-diphenylthiophene(2009) Manjunatha, M.G.; Vasudeva Adhikari, A.V.; Hegde, P.K.; Suchand Sandeep, C.S.; Philip, R.A new donor-acceptor type poly{2-(3,4-didecyloxythiophen-2-yl)-5-[3,4- diphenyl-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-1,3,4-oxadiazole} (P1) has been designed and synthesized starting from thiodiglycolic acid, 1,2-diphenylethane- 1,2-dione, and diethyl oxalate through multi-step reactions using precursor polyhydrazide route. The charge-transporting and linear optical property of the polymer has been investigated by cyclic voltammetric, UV-visible, and fluorescence emission spectroscopic studies. The UV-visible absorption spectrum of polymer in thin film form showed maxima at 420 nm. The polymer displayed bluish-green fluorescence both in solution and thin film form. The optical band gap is determined to be 2.27 eV. Third-order nonlinear optical property of the new polymer has been investigated at 532 nm using single beam Z-scan and degenerate four wave mixing (DFWM) techniques with nanosecond laser pulses. The absorptive nonlinearity observed for the polymer P1 is of optical limiting type, which arises due to an "effective" three-photon absorption (3PA) process. The third-order nonlinear optical susceptibility (?(3)) of the polymer is found to be 0.831 × 10-12 esu. Both linear and nonlinear optical studies revealed that the new polymer (P1) is a promising material for applications in photonic devices. © 2009 Springer Science+Business Media, LLC.Item Electrochemical and optical properties of a new donor-acceptor type conjugated polymer derived from 3,4-didodecyloxythiophene(Indian Academy of Sciences, 2010) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.In this communication, we report the synthesis and characterization of a new donor-acceptor type conjugated polymer carrying alternate 3,4-didodecyloxythiophene and (1,3,4-oxadiazol-yl)pyridine moieties and evaluation of its optical and electrochemical properties. The polymer was synthesized through precursor polyhydrazide route. It has well defined structure, stability and it shows good solubility in common organic solvents. Optical and electrochemical properties were studied by UV-visible, fluorescence spectroscopy and cyclic voltammetric studies, respectively. It displays bluish-green fluorescence both in solution and in film state. Cyclic voltammetric studies showed that the polymer P1 possesses a HOMO energy level of -6-01 and LUMO energy level of -3-34 eV. The preliminary studies clearly reveal that the new polymer can have potential application in the fabrication of light emitting diodes. The studies on its device application are in progress. © Indian Academy of Sciences.Item A novel narrow band gap red light-emitting cyanovinylene polymer derived from 3,4-dialkoxy thiophene for optoelectronic applications(Springer New York LLC journals@springer-sbm.com, 2010) Manjunatha, M.G.; Vasudeva Adhikari, A.V.; Hegde, P.K.A novel donor-acceptor type narrow band gap cyanovinylene poly{3,30-(3,4-ditetradecyloxythiene-2,5-diyl) bis[2-(thiophen-2-yl)prop-2- enenitrile]} has been designed and synthesized through multistep reactions. All the newly synthesized compounds were characterized by using FTIR and 1H NMR spectroscopy followed by elemental analyses. The polymer P is found to be thermally stable up to 300 °C under nitrogen atmosphere. The optical and charge-transporting properties of the polymer were investigated by UV-visible, fluorescence emission spectroscopic and cyclic voltammetric studies. The monomer (M) emits intense green-light in solution state and the polymer (P) exhibited intense red-fluorescence both in solution and solid state. The fluorescence quantum yield of the polymer is determined to be 43%. Cyclic voltammetric studies reveal that the polymer possesses good charge carrying property. The electrochemical band-gap is estimated to be 1.8 eV. The studies reveal that the new cyanovinylene polymer P is a promising material for the development of efficient optoelectronic devices. © Springer Science+Business Media, LLC 2009.
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