Journal Articles
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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 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 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 Optical and electrochemical properties of a new donor-acceptor type conjugated polymer derived from thiophene, carbazole and 1,3,4-oxadiazole units(Trans Tech Publications Ltd ttp@transtec.ch, 2010) Manjunatha, M.G.; Vasudeva Adhikari, A.V.; Hegde, P.K.A new donor-acceptor type poly[3-{5-[3,4-didecyloxy-5-(1,3,4-oxadiazol-2- yl)thiophen-2-yl]-1,3,4-oxadiazol-2-yl}-9-dodecyl-9H-carbazole] (P) has been synthesized starting from thiodiglycolic acid and 9H-carbazole through multistep reactions. The polymer has been synthesized through precursor polyhydrazide route. The weight average molecular weight of the polymer was found to be 7210. The polymer exhibited intense green fluorescence in solid sate. Cyclic voltammetric experiments showed that the polymer has low-lying LUMO (-3.55 eV) and high lying HOMO (-5.77 eV) energy levels due to the presence of alternate donor and acceptor units. The optical and electrochemical studies reveal that the new polymer (P) is a promising material for the development of polymer light emitting diodes (PLEDs). © (2010) Trans Tech Publications.Item Synthesis and characterization of a new NLO-active donor-acceptor-type conjugated polymer derived from 3,4-diphenylthiophene(2010) Manjunatha, M.G.; Vasudeva Adhikari, A.V.; Hegde, P.K.; Suchand Sandeep, C.S.; Philip, R.A new donor-acceptor-type conjugated polymer (P1) carrying 3,4-diphenylthiophene, 2,5-dihexyloxybenzene, and 1,3,4-oxadiazole units was synthesized through multistep reactions. The polymer was prepared using a polyhydrazide precursor route. The polymer has a well-defined structure and exhibits good thermal stability, with a decomposition onset temperature in nitrogen of 300 °C. Cyclic voltammetry experiments revealed that the polymer has low-lying LUMO (-3.68 eV) and high-lying HOMO (-5.78 eV) energy levels. The electrochemical band gap was found to be 2.10 eV. The UV-visible absorption spectrum of the polymer presented a maximum at 373 nm, and it displayed bluish-green fluorescence in dilute chloroform solution. The nonlinear optical properties of the new polymer were investigated at 532 nm using the Z-scan technique with nanosecond laser pulses. The polymer exhibited strong optical limiting behavior due to excited state absorption, which was phenomenologically similar to a three-photon absorption (3PA) process. The 3PA coefficient ? was found to be 7×10-22 m3/W2. The studies show that the new polymer (P1) is a promising material for developing efficient photonic devices.Item New diphenylamine-based donor-acceptor-type conjugated polymers as potential photonic materials(2011) Vishnumurthy, K.A.; Sunitha, M.S.; Philip, R.; Vasudeva Adhikari, A.V.A new series of donor-acceptor-type conjugated polymers (P1 and P2) carrying a diphenyl amine moiety were synthesized via Wittig condensation technique. The polymers structures were well established by FT-IR, 1H NMR, elemental analysis and gel permeation chromatographic techniques. They exhibited good thermal stability with an onset decomposition temperature of approximately 325 °C under nitrogen atmosphere. The optical and electrochemical properties of the polymers were studied by UV-vis, fluorescence emission spectroscopy and cyclic voltammetry. They exhibited good fluorescence in dilute solutions and showed solvatochromic behavior in various polar solvents. The electrochemical studies revealed that the polymers possess low-lying LUMO energy levels that ranging from -3.47 to -3.73 eV and high-lying HOMO energy levels that ranging from -5.57 to -5.81 eV. The thirdorder nonlinear optical properties of the polymers were investigated using the Z-scan technique. The effective two-photon absorption (TPA) coefficients (?) of the polymers were found to be 0.645 × 10-10 and 0.212 × 10-10 m/W. © 2011 Elsevier Ltd. All rights reserved.Item Synthesis and characterization of thiophene-based donor-acceptor type polyimide and polyazomethines for optical limiting applications(2013) Vishnumurthy, K.A.; Sunitha, M.S.; Vasudeva Adhikari, A.V.In this communication we describe the design and synthesis of four new conjugated polymers (P1-P4) based on 3,4-ditetradecyloxythiophene. The required diamine monomer was prepared by a unique catalyst-free reduction process using hydrazine hydrate. The structures of the intermediates and polymers were established by FTIR, 1H NMR spectroscopy. Molecular weights of polymers were determined by gel permeation chromatographic (GPC) method. Their electrochemical properties were investigated by cyclic voltammetry and linear optical properties were determined by UV-Visible absorption and fluorescence emission spectroscopic techniques. Further, their nonlinear optical properties were evaluated by Z-scan technique using Nd:YAG laser. These polymers showed strong optical limiting behavior with two-photon absorption (2PA) coefficients of the order of 10-10 m/W, which are comparable to that of good optical limiting materials reported in the literature. Also, it has been observed that the optical nonlinearity enhanced with the increase in donor-acceptor strength of the polymer backbone. © 2012 Springer-Verlag.Item New D-?-A type indole based chromogens for DSSC: Design, synthesis and performance studies(Elsevier Ltd, 2015) Babu, D.D.; Gachumale, S.R.; Anandan, S.; Vasudeva Adhikari, A.V.Three new Donor-?-Acceptor type dyes D1-3 carrying 3-(1-hexyl-1H-indol-3-yl)-2-(thiophen-2-yl)acrylonitrile as backbone with three different acceptor units were designed and synthesized as promising sensitizers for solar cell application. The new dyes were characterized using various spectral and elemental analyses. Their optical and electrochemical properties were investigated using spectrophotometry and cyclic voltammetry respectively, while their photovoltaic performance was evaluated by a device fabrication study. The devices were subjected to electrochemical impedance spectroscopy to gain an insight into the interfacial charge transfer and recombination process while in use. Further, density functional theory study was carried out to investigate their Frontier Molecular Orbital energy states. The study reveals that the dye carrying 4-aminobenzoic acid as an acceptor showed the highest photovoltaic efficiency among the three dyes. This can be attributed to the longer electron lifetime and lower recombination rates. Additionally, a Single crystal X-ray diffraction study confirmed the structure of a key intermediate. © 2014 Elsevier Ltd. All rights reserved.Item Synthesis, physicochemical properties and computational study of donor–acceptor polymer for optical limiting application(Springer Nature, 2020) Vishnumurthy, K.A.; Girish, K.H.; Vasudeva Adhikari, A.V.A new donor–acceptor configured ?-conjugated polymer P1 with alkoxy pendant groups having cyclic diimide and thiophene core moieties in polymer backbone were efficiently synthesized via polycondensation reaction. The incorporation of cyclic diimide in polymer increased the rigidity and thermal stability of polymer backbone aided by its high Tg value. These chromophores assisted in reducing the steric interaction of bulky alkoxy pendants which supported lowering the bandgap. The donor and acceptor moieties along with ? spacers were particularly chosen to enhance the ?-conjugation length in the polymer thereby increasing its nonlinear optical absorption i.e. two-photon absorption. The various structure–property relationships of the polymer were characterized by UV–Vis absorption, fluorescence emission, cyclic voltammetry, and density functional theory studies. The molecular nonlinear properties were theoretically evaluated through the calculation of polarizabilities and hyperpolarizabilities using time-dependent Hartree–Fock method. The polymer showed enhanced effective two-photon absorption with an absorption coefficient (?eff) of 2.031 × 10?10 m/W obtained from open aperture Z-scan analysis which is in good agreement with theoretical study. © 2020, Springer Nature Switzerland AG.