Faculty Publications
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Item Nonlinear optical studies on a new poly{2-(biphenyl-4-yl)-5-[3,4- didecyloxy-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-1,3,4-oxadiazole}(Trans Tech Publications Ltd ttp@transtec.ch, 2010) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.; Suchand Sandeep, C.S.; Philip, R.Measurements of nonlinear optical properties of a newly synthesized thiophene based polymer are reported. The nonlinear transmission measurements were performed on the polymer dissolved in N,N-dimethylformamide by employing the single beam Z-scan technique using a Q-switched laser output at 532-nm. The polymer shows strong optical limiting behavior, where the transmittance decreases when the pump fluence is increased. It was found that an effective three-photon absorption (3PA) model at the excitation wavelength gives the best fit to the obtained experimental data. The value of the 3PA coefficient has been numerically calculated. This study clearly reveals the potential of new polymeric material has, for optical limiting applications. © (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 Synthesis and third order optical nonlinearity studies of the donor-acceptor conjugated polymer, poly(2-[3,4-didodecyloxy-5-(1,3,4-oxadiazol- 2-yl)thiophen-2-yl]-5-phenyl-1,3,4-oxadiazole) and a polymer/TiO2 nanocomposite(2010) Murali, M.G.; Ramya, M.G.; Udayakumar, D.; Lakshmi, N.B.; Philip, R.A donor-acceptor conjugated polymer (PDOThPOD) containing 3,4-didodecyloxythiophene and (1,3,4-oxadiazolyl)benzene units is synthesized by using precursor polyhydrazide route. Cyclic voltammetry studies reveal that the polymer possesses a low-lying LUMO energy level (-3.57 eV). A nanocomposite of polymer PDOThPOD and nano TiO2 is also prepared. The linear optical properties of PDOThPOD and the nanocomposite are studied using UV-vis absorption spectroscopy and fluorescence emission spectroscopy. z-scan technique is used to study the third order nonlinear optical properties of the polymer and nanocomposite films. Both polymer and nanocomposite films show a strong optical limiting behavior. The value of nonlinear absorption coefficient (?) is found to be of the order of 10-7 m/W, indicating that these materials are potentially suited for fabricating optical limiters. © 2010 Elsevier B.V. All rights reserved.Item Novel poly(3,4-dialkoxythiophene)s carrying 1,3,4-oxadiazolyl-biphenyl moieties: Synthesis and nonlinear optical studies(2011) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.; Suchand Sandeep, C.S.; Philip, R.Two new donor-acceptor types of polymer, poly{2-(biphenyl-4-yl)-5-[3,4-dialkoxy-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-1,3,4-oxadiazole}s, were synthesized starting from 2,2'-sulfanediyldiacetic acid and diethyl ethanedioate through multi-step reactions. The polymerization was carried out via the polyhydrazide precursor route. The optical and charge-transporting properties of the polymers were investigated using UV-visible and fluorescence emission spectroscopic and cyclic voltammetric studies. The polymers showed bluish-green fluorescence in solutions. The electrochemical band gaps of the polymers were determined to be 2.16 and 2.22 eV. The nonlinear optical properties of the polymers were investigated at 532 nm using the single-beam Z-scan technique with nanosecond laser pulses. The polymers showed strong optical limiting behaviour due to effective three-photon absorption. The values of the three-photon absorption coefficients for the polymers were found to be 9 × 10-24 and 17 × 10-24 m3 W-2, which are comparable to those of good optical limiting materials. © 2010 Society of Chemical Industry.Item Design and synthesis of a new thiophene based donor-acceptor type conjugated polymer with large third order nonlinear optical activity(2011) Vishnumurthy, K.A.; Vasudeva Adhikari, A.V.; Sunitha, M.S.; Ann Mary, K.A.A.; Philip, R.In this communication we describe the design and synthesis of a new conjugated polymer (P) carrying 3,4-dialkoxythiophene, 1,3,4-oxadiazole and thienylene-vinylene units, from its monomers using Wittig condensation method. The structure of newly synthesized polymer was confirmed by FT-IR, 1H NMR, UV-vis spectral, elemental analysis and gel permeation chromatographic techniques. The polymer exhibited good thermal stability with the onset decomposition temperature around 320 °C in nitrogen atmosphere. Further, its electrochemical, linear and nonlinear optical properties have been investigated. The optical and electrochemical band gap was found to be 2.21 eV. Its third-order nonlinear optical property was investigated by Z-scan and DFWM techniques, using a Q-switched, frequency doubled Nd:YAG laser producing 7 ns laser pulses at 532 nm. Z-scan results reveal that the polymer exhibits self-defocusing nonlinearity. The operating mechanism involves reverse saturable absorption. The polymer shows strong optical limiting behavior due to effective two-photon absorption (2PA). The value of 2PA coefficient was found to be 3.0 × 10-11 mW, which is comparable to that of good optical limiting materials. The fluorescence quantum yield of the polymer in solution was determined using quinine sulfate as standard and it was found to be 35%. © 2011 Elsevier B.V. All rights reserved.Item Synthesis, electrochemical and optical studies of new cyanopyridine based conjugated polymers as potential fluorescent materials(Elsevier Ltd, 2011) Vishnumurthy, K.A.; Sunitha, M.S.; Safakath, K.; Philip, R.; Vasudeva Adhikari, A.V.In this communication we describe the design and synthesis of four new conjugated polymers (P1-P4) carrying cyanopyridine in their backbone via Wittig condensation technique. Their structures were well established by FTIR, 1H NMR, elemental analysis and gel permeation chromatographic techniques. They exhibited good thermal stability with the onset decomposition temperature around 300-350 °C in nitrogen atmosphere. Further, their electrochemical, linear and third-order non-linear optical properties have been investigated. The polymers showed low electrochemical band gaps in the range of 1.77-1.99 eV and displayed very good fluorescence emission property in various polar solvents. The fluorescence quantum yields of polymers P1-P4 in tetrahydrofuran (THF) were found to be 35, 42, 38 and 34%, respectively. The effective two-photon absorption coefficients (?) for the polymers were determined by Z-Scan technique and were found to be 1.34 × 10 -11, 1.24 × 10-11, 3.04 × 10-11 and 1.85 × 10-11 m/W for polymers P1-P4, respectively. © 2011 Elsevier Ltd. All rights reserved.Item Nonlinear optical characterization of new thiophene-based conjugated polymers for photonic switching applications(2011) Hegde, P.K.; Vasudeva Adhikari, A.V.; Manjunatha, M.G.; Suchand Sandeep, C.S.S.; Philip, R.This research article describes a technique to synthesize new donor-acceptor-type conjugated polymers carrying 1,3,4-oxadiazolyl-naphthalene and 3,4-(ethylenedioxy/diphenyl)-thiophene moieties (P1 and P2) starting from 2,2?-sulfanediyldiacetic acid and diethyl ethanedioate through multistep reactions. The newly synthesized intermediates and the final polymers have been characterized by different spectroscopic techniques followed by elemental analysis. Their optical and electrochemical properties have been investigated by UV-visible, fluorescence spectroscopy, and cyclic voltammetric studies, respectively. Furthermore, the nonlinear optical transmission properties of these polymers have been investigated by the open aperture z-scan technique. The new polymers P1 and P2 have well-defined structures, good thermal stability, and band gaps of 1.98 and 1.88 eV, respectively. They emit bluish-green fluorescence both in solution and in film state. Interestingly, these polymers show saturable absorption behavior. The results of nonlinear optical studies reveal that they are potential candidates for photonic switching device applications. © 2011 Wiley Periodicals, Inc.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 Large third-order nonlinearity of new ?-conjugated donor-acceptor polymers with substituted thiophene and 1,3,4-oxadiazole moieties(2012) Sunitha, M.S.; Vasudeva Adhikari, A.V.; Vishnumurthy, K.A.; Safakath, K.; Philip, R.We present the synthesis of two newly designed, thiophene-based conjugated polymers (P1 and P2) carrying 1,3,4-oxadiazole, 3,4-dinaphthyloxy thiophene, and 3,4-dialkoxy thiophene moieties as potential NLO active materials. Their NLO properties have been investigated both by the Z-scan and degenerate four-wave mixing (DFWM) techniques using 532nm, 7 nanosecond laser pulses. The measured ? and ?(3) values for the polymers are found to be in the range of 1011m/W and 1011esu, respectively. The results indicate that they exhibit good optical-limiting behavior and are promising materials for nonlinear optical applications due to effective two-photon absorption (TPA). © 2012 Copyright Taylor and Francis Group, LLC.