Faculty Publications
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Item Synthesis, characterization and third-order nonlinear optical studies of copper complexes containing 1,10-phenanthroline-5,6-dione and triphenylphosphine ligands(2011) Rudresha, B.J.; Badekai Ramachandra, B.; Sampath Kumar, H.C.; Shivakumar, K.I.; Safakath, K.; Philip, R.This research article describes the synthesis, characterization and third-order nonlinear optical studies of copper(I) complexes [Cu(Br)(N,N?-C12H6N2O2) (PPh3)] and [Cu(I)(N,N?-C12H6N 2O2)(PPh3)] abbreviated as [CuBrLPPh 3] (1) and [CuILPPh3] (2) (L = 1,10-phenanthroline-5,6- dione). Nonlinear optical properties of the complexes are investigated at 532 nm using single beam Z-scan and degenerate four-wave mixing (DFWM) techniques employing nanosecond laser pulses. The complexes show optical limiting behaviour due to "effective" two-photon absorption. The values of the effective two-photon absorption (2PA) coefficients (?), third-order nonlinear susceptibilities (?(3)), and figures of merit (F), are calculated. © 2010 Elsevier B.V. All rights reserved.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 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.Item Nonlinear transmittance and optical power limiting in magnesium ferrite nanoparticles: effects of laser pulsewidth and particle size(Royal Society of Chemistry, 2016) Perumbilavil, S.; Sridharan, K.; Abraham, A.R.; Janardhanan, H.P.; Kalarikkal, N.; Philip, R.We report comparative measurements of size dependent nonlinear transmission and optical power limiting in nanocrystalline magnesium ferrite (MgFe2O4) particles excited by short (nanosecond) and ultrashort (femtosecond) laser pulses. A standard sol-gel technique is employed to synthesize particles in the size range of 10-50 nm, using polyvinyl alcohol as the chelating agent. The structure and morphology of the samples are studied using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Growth of the particles in time is tracked through Fourier transform infrared spectroscopy. Nonlinear transmission measurements have been carried out using the open aperture Z-scan technique employing 532 nm, 5 nanosecond pulses and 800 nm, 100 femtosecond pulses, respectively. The measured optical nonlinearity is primarily of a reverse saturable absorption (RSA) nature, arising mostly from excited state absorption for nanosecond excitation, and two-photon absorption for femtosecond excitation. The optical limiting efficiency is found to increase with particle size for both cases. The calculated nonlinear parameters indicate that these materials are potential candidates for optical limiting applications. © The Royal Society of Chemistry.Item Ultrafast and short pulse optical nonlinearity in isolated, sparingly sulfonated water soluble graphene(Elsevier Ltd, 2017) Perumbilavil, S.; Sridharan, K.; Koushik, D.; Sankar, P.; MahadevanPillai, V.P.M.; Philip, R.We report the nonlinear optical properties of graphene oxide (GO), reduced graphene oxide (rGO), sulfonated graphene oxide (S-rGO), and sparingly sulfonated water soluble graphene (WSG), measured under ultrafast (100 fs) and short pulse (300 ps, 50 ns) laser excitations at 800 nm, employing the open aperture Z-scan technique. The samples exhibit typical third order nonlinear optical behaviour including two-photon absorption (2 PA), reverse saturable absorption (RSA), and saturable absorption (SA). A significant variation in the nature of nonlinear absorption is seen when the laser pulse duration is changed. For example, RSA is prominent under nanosecond (ns) excitation, 2 PA is prevalent under femtosecond (fs) excitation, and SA is dominant under picosecond (ps) excitation. For comparison purposes the measurements are repeated using 5 ns laser pulses at 532 nm. RSA is enhanced in WSG in the nanosecond excitation domain, which can be attributed to the covalent bonding between p-phenyl-SO3H groups and sp2 graphitic planes. WSG exhibits a switching behaviour from SA to RSA upon increasing the excitation intensity under fs excitation. Results show that these graphene derivatives are potentially useful for saturable absorber and optical limiter device applications. © 2016 Elsevier Ltd