Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors

the thesis entitled “Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors” portrays our attempts to explore the solvent, concentration and temperature effect of the reaction between a few (anthracen-9- yl)methanamines with electron acceptors like DMAD, DBA and DBE. We have also studied the effect of solvent and percentage fluorescence quenching in the photoinduced electron transfer reactions of these ‘donor-spacer-acceptor’ systems. Finally we look in to the intramolecular electron transfer reactions of a few tertiary amine appended dibenzobarrelenes and bisdibenzobarrelenes

Phenylethynylarene Based Donor-Acceptor Systems: Design, Synthesis and Photophysical Studies

This thesis Entitled phenylethynylarene based Donor-Acceptor systems:Desigh,Synthesis and Photophysical studies. A strategy for the design of donor-acceptor dyads, wherein decay of the charge separated (CS) state to low lying local triplet levels could possibly be prevented, is proposed. In order to examine this strategy, a linked donor-acceptor dyad BPEPPT with bis(phenylethYlly/)pyrene (BPEP) as the light absorber and acceptor and phenothiazine (PT) as donor was designed and photoinduced electron transfer in the dyad investigated. Absorption spectra of the dyad can be obtained by adding contributions due 10 the BPEP and PT moieties indicating that the constituents do not interact in the ground stale. Fluorescence of the BPEP moiety was efficiently quenched by the PT donor and this was attributed to electron lransfer from PT to BPEP. Picosecond transient absorption studies suggested formation of a charge separated state directly from the singlet excited state of BPEP. Nanosecond flash photolysis experiments gave long-ived transient absorptions assignable to PT radical cation and BPEP radical anion. These assignments were confirmed by oxygen quenching studies and secondary electron transfer experiments. Based on the available data, energy level diagram for BPEP-PT was constructed. The long lifetime of the charge separated state was attributed to the inverted region effects. The CS state did not undergo decay to low lying BPEP triplet indicating the success of our strategy

An Optical limiter based on Ferrofluids

We report an optical limiter based on ferrofluids which has a very high shelf life and remarkable thermal stability, which are important requirements for sustainable use with intense lasers. The colloidal suspensions contain nanosized particles of approximately 80 Å diameter, with a number density of the order of 1022 /m3. The nonlinear optical transmission of the samples is studied using nanosecond and femtosecond laser pulses. Excited state absorption phenomena contribute to enhanced limiting in the nanosecond excitation regime. An advantageous feature of ferrofluids in terms of device applications is that their optical properties are controllable by an external magnetic field.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Visible luminescence mechanism in nano ZnO under weak confinement regime

We describe the structure of luminescence spectrum in the visible region in nano-ZnO in colloidal and thin film forms under weak confinement regime by modeling the transition from excited state energy levels of excitons to their ground state. Measurements on nanocrystallites indicate the presence of luminescence due to excitonic emissions when excited with 255 nm. The relevant energy levels showing the transitions corresponding to the observed peaks in the emission spectrum of ZnO of particle size 18 nm are identified.

Investigation of nonlinear absorption and aggregation in aqueous solutions of rhodamine B using thermal lens technique

Thermal lensing effect was studied in aqueous solutions of rhodamine B using 532 nm, 9 ns pulses from a Nd:YAG laser. A low intensity He-Ne laser beam was used for probing the thermal lens. Results obtained show that it is appropriate to use this technique for studying nonlinear absorption processes like two photon absorption or excited state absorption and for analyzing dimerization equilibria.

Third order nonlinear optical studies in europium naphthalocyanine using degenerate four wave mixing and Z-scan

Third order nonlinear susceptibility χ(3) and second hyperpolarizability (γ) of a bis-naphthalocyanine viz. europium naphthalocyanines, Eu(Nc)2, were measured in dimethyl formamide solution using degenerate four wave mixing at 532 nm under nanosecond pulse excitation. Effective nonlinear absorption coefficient, βeff and imaginary part of nonlinear susceptibility, Im(χ(3)) were obtained using open aperture /Z-scan technique at the same wavelength. Optical limiting property of the sample was also investigated. The role of excited state absorption in deciding the nonlinear properties of this material is discussed.

Solvent Effect on Absolute Fluorescence Quantum Yield of Rhodamine 6G Determined Using Transient Thermal Lens Technique

Dual beam thermal lens tecbnique is successfully employed for the determination of absolute Fluorescence quantum yield of rhodamine 6G lnser dye in different solvents. A 532 nm radiation from a Q-switched Nd:YAG laser was used for the excitation purpose. The fluorescence quantum yield values are found to be strongly influenced by environmental effects. It has been observed that fluorescence yield is greater for rhodamine 6G in ethylene glycol system than in water or in methanol. Our results also indicate that parameters like concentration of the dye solution, aggregate formation and excited state absorption affect the absolute values of fluorescence yield significantly.

A Study of Photoacoustic Effects and Optical Limiting in the Solution of C60 in Toluene

Pulsed photoacoustic studies in solution of C60 in toluene have been made using the 532 nm radiation from a frequency doubled Nd:YAG laser. Though C60 is found to exhibit the phenomenon of optical limiting, the results on photoacoustic measurements do not give any indication of multiphoton transitions as suggested in some of the earlier works. Results of photoacoustic measurements show that excited state absorption is the dominant process responsible for optical limiting while phenomena like nonlinear scattering may contribute to a lesser extent.

Nanosecond optical limiting response of sandwich-type neodymium dyphthalocyanine in a co-polymer host

The nanosecond optical limiting characteristics of sandwich-type neodymium diphthalocyanine in a co-polymer matrix of polymethyl methacrylate (PMMA) and methyl-2-cyanoacrylate have been studied for the first time. The measurements were performed using 9 ns laser pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The optical limiting performance of neodymium diphthalocyanine in co-polymer host was studied at different linear transmission. Laser damage threshold was also measured for the doped and undoped co-polymer samples. The optical limiting response is attributed to reverse saturable absorption which is due to excited-state absorption.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.

Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes

The thesis entitled: ‘Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes’ is divided into 5 chapters.In Chapter 1, the fundamental concepts of Diels-Alder reaction, di-r:methane rearrangement and energy transfer process in organic photochemistry is discussed.Chapter 2 presents the synthesis of 9-olefin appended anthracenes and bisanthracenes. The target of synthesising various bridgehead olefin appended dibenzobarrelenes and some novel bisdibenzobarrelenes, led us to the synthesis of the appropriate alkenylanthracenes and bisanthracenes as precursor molecules. Diels-Alder reaction was the synthetic tool for the preparation of the target olefin appended dibenzobarrelenes and bisdibenzobarrelenes. This chapter attempts to throw light on our endeavours in synthesising the various 9-alkenylanthracenes and bisanthracenes.Chapter 3 deals with the synthesis of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Ever since the discovery of di-It-methane rearrangement dibenzobarrelenes, tailored with dijferent substituents at various positions have always been a tool to photochemists in unravelling the mechanisms of light induced reactions. Our intention of analysing the role of a It-moiety at the bridgehead position of the dibenzobarrelene, was synthetically envisaged via the Diels-Alder reaction. Bisdibenzobarrelenes were synthesised through tandem Diels-Alder reaction. Various alkenylanthracenes and bisanthracenes were employed as dienes and the dienophiles used were dimethyl acetylenedicarboxylate and dibenzoylacetylene. In this chapter, we report our venture in synthesising the various olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Chapter 4 describes the preliminary time-resolved fluorescence studies of some olefin appended dibenzobarrelenes and bisdibenzobarrelenes.To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes.Chapter 5 portrays the photochemistry of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Dibenzocyclooctatetraene and dibenzosemibullvalene are the photoproducts obtained respectively through the singlet excited state and the triplet excited state of dibenzobarrelenes. Chemical literature shows evidences of the photoreactivity of dibenzobarrelenes generating both the singlet and triplet mediated photoproducts, in a single photoreaction. Our research target in synthesising various bridgehead olefin appended dibenzobarrelenes and bisdibenzobarrelenes, was based on the perception that olefins are eflicient triplet quenchers, thereby quenching intramolecularly the triplet excited state of the barrelenes. A It-moiety at the bridgehead position of the dibenzobarrelene, creates a tetra tr-methane system, which similar to a 6li—7l' or tri-tr-methane systems, could be the fertile ground for interesting photochemical rearrangements. Our attempts in deciphering the photochemistry of the olefin appended dibenzobarrelenes and bisdibenzobarrelenes is the substance of this chapter.

Characteristics of a Microstrip-Excited High-Permittivity Tectangular Dielectric Resonator Antenna

The radiation characteristics of a microstrip-line-excited rectangular dielectric resonator antenna (DRA) are studied experimentally.The radiation charactristics and excitation of different modes are highly influenced by the orientation of the DR,feed line parameters ,and finite size of the ground plane