Using two different model systems, this thesis considers the old, but fascinating question: how do atoms or particles possessing a particular set of individual characteristics combine to form assemblies with quite distinct, ensemble characteristics, and how do those characteristics evolve as a function of the size of the assembly? For the last thirty years, numerous experiments studying the emergence of collective material properties have focused on a class of semiconducting, colloidal nanocrystals commonly known as quantum dots, which are notable for the size-dependence of their optical properties. Despite years of effort, even the most uniform quantum dot samples possess some heterogeneity in size, shape, and composition, which has prevented complete structure determination and hindered understanding of structure-property relationships. Chapter 1 of this thesis presents an approach to overcoming this challenge and reports the synthesis of a set of four, new, atomically precise cadmium selenide nanocrystal samples, which we call CdSe(350 nm), CdSe(380 nm), CdSe(408 nm), and CdSe(435 nm) after their lowest energy absorption features. We determine their structures and formulas through a combination of single crystal and powder X-ray diffraction measurements, elemental analysis, and spectroscopy. We also describe the optical properties of these samples and their sensitivity to ligand coverage, compare them to other previously reported cadmium selenide nanomaterials, and discuss ongoing experiments. Because CdSe(350 nm), CdSe(380 nm), CdSe(408 nm), and CdSe(435 nm) are atomically precise, they allow us to correlate specific structural features with material properties, which is the focus Chapter 2. Here we present a series of Raman scattering experiments designed to probe the evolution of vibrational structure with size. We find that the Cd-Se stretching region of the Raman spectra exhibits two peaks, which are assigned to primarily surface-derived and interior-derived atomic motions using density functional theory calculations. By performing variable temperature measurements, we discover that the smallest sample, CdSe(350 nm), exhibits behavior that can be well-described using a model developed for small molecules while the vibrations of the largest measured cluster, CdSe(408 nm), are better described by a model developed for bulk materials. This observation is evidence that the transition to a more bulk-like vibrational structure occurs relatively rapidly when cadmium selenide materials are approximately 2 nm in size. The emergence of collective material properties is also the subject of Chapter 3, but the topic is approached from a different perspective. Instead of focusing on a series of atomically precise clusters that differ in size, Chapter 3 presents a series of molecules composed of atomically precise clusters. We prepare octahedral hexaruthenium carbonyl clusters, [Ru₆C(CO)₁₆]²⁻, and use them as building blocks to assemble oligomers linked by single metal atom bridges. We synthesize and structurally characterize a set of compounds varying in length (from monomer to trimer) and linker atom identity (cadmium and mercury) and study the effect on electronic structure using infrared and UV-Visible absorption spectroscopies and density functional theory calculations. With increasing oligomer length, the UV-Vis absorption profile changes and shifts to lower energy, which we attribute in part to the development of coupling between neighboring clusters. Our calculations show that the infinite polymer composed of [Ru₆C(CO)₁₆]²⁻ linked by Hg²⁺ would be a one-dimensional semiconductor with a 1.5 eV direct band-gap. More detailed abstracts can be found at the beginning of each chapter.

The present thesis is focused on rational design and synthesis of π-conjugated donoracceptor-donor (D-A-D) type oligomers and D-A type copolymers. Thesis is organized in seven chapters, apart from introduction remaining six chapters are grouped into two parts (A and B). Part A deals with Chapters 2, 3, 4 and Part B contains chapters 5, 6 and 7. A brief discussion on the content of individual chapters is provided below. Chapter 1 discusses the introduction to organic solar cell with operating principles and effect of spinodal decomposition on stability of the devices is presented. The status and literature related to the improvement of life time of the organic solar cells by self-assembly approach has been explored. In addition, design and synthesis of the fluorine substituted π-conjugated organic semiconductors for n-type OFETs and OLED has been discussed. Part A This part of the thesis attempt to address some of the challenges listed below (1) Investigation of miscibility of binary components in bulk heterojunction solar cells through H-bonding approach. (2) Synthesis of new low band gap molecular semiconductors having H-bonding sites. (3) Fabrication of bulk heterojunction solar cell devices using these new molecules and exploring the photovoltaics performance. Chapter 2, donor-acceptor-donor (D-A-D) concept has been employed to design low band gap oligomers named as TTB. Barbiturate functional group has been utilized to explore the concepts of supramolecular chemistry. It is shown that, TTB molecule self-organizes via intermolecular H-bonding between barbituric acid units. Interactions between the oligothiophene subunits were also found to be important, affording nanoribbons that were observed by atomic force and transmission electron microscopy. The applicability of TTB for organic electronic applications was investigated by fabricating organic field-effect transistors (OFETs) and organic photovoltaic device. The crystalline nanoribbons were beneficial in understanding the phase morphology of PCBM and TTB blend. Chapter 3, the self-assemble property of TTB was disrupted by the substitution of methyl group on the nitrogen of the barbituric acid moiety. The optical and electrochemical properties of the new derivative have been investigated by UV-Visible spectroscopy, photoluminescence spectroscopy and cyclic voltammetry. Further investigations on the effect of self-assembly on organic solar cells were carried out by fabricating BHJ and OFET. The results proved that the self-assembly within the donor moieties led to complete phase separation between the donor and acceptor which had an adverse effect on the photovoltaic performance. Chapter 4, the conjugation of TTB was extended by the synthesis of two new copolymers by polymerizing with two oliogothiophene (terthiophene and benzobithiophene) derivatives with different donating strength. The investigation of photophysical and electrochemical properties of copolymers were studied by varying the donating strength. As we increase the donating strength of oligothiophenes, the intramolecular charge transfer band of DA copolymers was red shifted. Further, density functional theory (DFT) calculation of these materials was carried out to get insight into their photophysical properties. Part B This part of the thesis attempt to address some of the challenges listed below (1) Investigation of fluorine substituted organic semiconductos like 2,2’ bithiazole and pheanthroimidazole. (2) Synthesis of pentafluoro phenyl appended derivatives of 2,2’ bithiazole and pheanthroimidazole. (3) Fabrication of OFETs and OLEDs using these new molecules and elucidated the device performance with molecular structure. Chapter 5, pentafluorophenyl appended 2,2’-bithiazole derivatives were synthesized. The single crystal x-ray diffraction studies shows the unusual strong type-II F•••F interactions within the distance of 2.668 Å, at an angle of 89.14° and 174.15°. It also shows the usual type-I F•••F interaction within the distance of 2.825Å, at an angle of 137.38° and 135.93°. Upon bromination type-II Br•••Br interaction was observed and the packing was further stabilized by S•••Br interactions. The conjugation was further extended with different aromatic and heteroaromatic substituents and synthesized the star shaped structure. The band gap as well as the electronic energy levels was tuned by substituting various aromatic and heteroaromatic substituents. These star shaped derivatives shows electron mobilities in the order of 10-4 to 10-3cm2/Vs. Chapter 6, Novel D-A copolymers were synthesized by Stille condensation of electron acceptor fluorinated phenanthroimidazole with electron donors like terthiophene and benzobithiophene. Prior to that insoluble pentafluoro phenyl phenanthroimidazole was Nalkylated in presence of DMF which concurrently resulted in C-F activation of the pentafluoro phenyl moiety. As we increase the donor strength from benzobithiophene to terthiophene the absorbance spectra was red shifted from 446 nm to 482 nm in solution and 455 nm to 484 nm in solid state. The band gap of these copolymers was found to be 2.4 eV for PIBDT and 2.2 eV for PIDHTT from the absorbance spectra. The photoluminescence data shows that these materials are promising for the yellow colour as well as orange colour displays, of narrow wavelength range (FWHM 40 nm for PIBDT and 35 nm for PIDHTT), which can be achieved just by the manipulation of donor moieties in the copolymers. The preliminary electroluminiscence data shows high brightness of 888cd/m2 (orange luminescence) for PIDHTT and 410cd/m2 (yellow luminescence) for PIBDT. Chapter 7, Acenaphtho[1,2-b]quinoxaline based donor–acceptor type low band gap conjugated copolymers were synthesized by Stille coupling reaction with the corresponding oligothiophene derivatives. The optical properties of the copolymers were characterized by ultraviolet-visible spectrometry while the electrochemical properties were determined by cyclic voltammetry. The band gap of these polymers was found to be in the range of 1.8-2.0 eV as calculated from the optical absorption band edge. The intense charge transfer band in absorption spectra shows the significant effect of acceptor in the copolymers. X-ray diffraction measurements show weak π–π stacking interactions between the polymer chains. The OFET devices fabricated using these co-polymers showed dominant p-channel transistor behavior with the highest mobility of 1×10-3cm2/Vs.

Chapter 1: Amphiphilic self-assembled systems as nanocarriers Nanocarriers are the nanometric size molecular assemblies that are used for the transport of small molecules into their non-solvating environments. These systems find major applications as drug delivery systems (DDS) in pharmacological research. These drug delivery systems improves solubility and stability of the drug molecules through encapsulation and also offer additional advantages like target specificity and stimuli responsive release of the drug molecules. Several types of DDS are reported in the literature, which can be prepared by a variety of processing techniques. Of these, molecular self- Chart 1: Developments in the design of amphiphilic nanocarriers assembly has attained considerable attention due to its greater tunability and control in the preparation of nanocarriers. In this chapter we discussed about the amphiphilic nanocarriers which are prepared through self-assembly of amphiphiles through hydrophobic interactions. Several developments in the area of amphiphilic nanocarriers such as di-block polymeric systems, dendritic systems and core-shell architectures are also mentioned. We also highlighted some recent developments in the design of amphiphilic nanocarriers through supramolecular interactions and advantages of such systems. Chapter 2: Bile acid derived dendrons and their application as nanocarriers Host-guest chemistry is well known for dendritic systems. To understand the influence of steric crowding, dendritic effect and importance of number of hydroxyl groups on the bile acid backbone in the host-guest chemistry of bile acid dendrons, we designed and synthesized a new series of C3 symmetric systems and studied the above-mentioned objectives through extraction of polar dyes into nonpolar media. Dye extraction experiments performed using trimeric molecules suggested that only the cholate derivatives (3 and 4) showed considerable extraction of the polar dyes into chloroform; deoxycholate derivatives did not show any extraction, thus emphasizing the importance of the number of hydroxyl groups for dye extraction in these molecular architectures. The effect of steric crowding at the core of these trimeric molecules was shown by efficient extraction of the dyes with the triethylbenzene core (4) compared to the benzene core (3). Greater influence of the aggregates in the case of triethylbenzene core on the extracted dye was also manifested in the Chart 2: Structures of the designed molecules 1-6 value of the induced circular dichroism signal. Surprisingly, a higher analogue in these molecular architectures showed lesser efficiency in dye extraction (on a per bile acid residue basis) compared to the trimers, suggesting a more compact structure for the higher analogue. This was supported by molecular modeling studies. Generality of these systems as nanocarriers for hydrophilic dyes was investigated by screening several other dyes and polar molecules, which are diverse in their structure and functionalities. All these experiments suggested a dependency of the extraction profile on the size of the dye molecule. This was also examined by dynamic light scattering studies, which showed larger size and wider distribution in the size of the aggregates in the case of larger dyes. We also demonstrated selective extraction of a single dye molecule from a blended food color (apple green) using one of the trimer (4) and demonstrated solvent dependent morphological changes in these compounds using electron microscopy. The self-assembly of these amphilic molecules at the air-water interface was studied through Langmuir monolayer studies. Chart 3: Structure of polar guest molecules (Cresol red (7). Erioglaucine (8), Eriochrome black T (9),) phenyl β-D-glucopyranoside (10) and Eosin B (11) Chapter 3: Design and synthesis of bile acid derived surfactants: Study of their aggregation and potential applications Bile acids are facially amphiphilic systems and their amphiphilicity can be improved by attaching polar groups on the bile acid back bone or by synthesizing oligomeric systems which show better self-assembly compared to their monomeric units. To study and improve the amphiphilicity of bile acids, we designed and synthesized a new tripodal surfactant system, with a phosphine oxide based central core to which the bile acids were attached through the C-3 position using click chemistry. Our molecular design also offers added advantage of studying the influence of the stereochemistry at the C-3 position on the aggregation of these molecular architectures. We synthesized trimeric systems with both cholic and deoxycholic acids attached to the central phosphine oxide core with α and β stereochemistry at the C-3 position. Aggregation of these molecules was studied by surface tension measurements, dye extraction studies and NMR. All these compounds showed aggregation at micromolar concentrations. NMR studies suggested changes in the structure of the aggregates at higher temperature and these changes were studied by DLS, which suggested thermodynamically stable monodispersed aggregates for cholic acid derivatives (13 and 15) at higher temperature. These aggregates are stable even after cooling to room temperature and with time. The aggregates of these derivatives were also characterized by atomic force microscopy. Gelation was observed in the case of α derivatives (12 and 13) in phosphate buffer (0.1 M) at pH 7.5 for both deoxy and cholic derivatives, which emphasized the influence of stereochemistry at C-3 position in these architectures. These gels were characterized by rheology experiments. Finally, the possible utility of these micellar systems as model systems to study photophysical processes was demonstrated through lanthanide sensitization experiments in these micellar solutions. Chart 4: Structure of the designed molecules Chapter 4: Synthesis of oligomeric bile acid-taurine conjugates: Study of their aggregation and efficiency in cholesterol solubilization Bile acids are bio-surfactants that are used for the emulsification of fats, vitamins etc. in our body. Bile salts also solubilize the excess cholesterol in our body through mixed micelle formation in the bile and when the bile gets saturated with cholesterol, it leads to cholesterol gallstone formation, which needs to be treated. Ursodeoxycholic acid (UDCA) is used as drug in some cases for the solubilization of (small) cholesterol gallstones, even though the efficiency to solubilize cholesterol is less for UDCA compared to the other bile acids (UDCA is less toxic than the others). So there is a need to develop new cholesterol solubilizing agents. Since oligomeric systems can aggregate better, we designed and synthesized two tetramer taurine conjugates, which differ in the spacer between the bile acid units. Since these conjugates are not soluble in water, their solubility and aggregation was studied in 10% MeOH/Water using pyrene fluorescence experiments. Aggregation studies suggested better aggregation for these molecules compared to their monomeric analogues. These aggregates were also characterized byDLS and electron microscopy. These systems were subsequently studied as nanocarriers for liphophilic dye molecules into aqueous media. Finally, the influence of oligomeric effect in cholesterol solubilization was investigated by cholesterol solubilization studied using these two tetramer taurine compounds and a control, sodium taurocholate. These studies suggested efficient solubilization of cholesterol by oligomers compared to monomeric analogues.(For structural formula pl see the abstract file)

Functional Dendritic Structures from Bile Acids: Supramolelcular Hosts, Light Harvesters and Drug Carriers Chapter 1. An Overview of Functional Dendrimers. Dendrimers are welldefined, hyperbranched macromolecules that are prepared by highly controlled iterative methodologies. The ability to modulate the size, molecular weight, chemical functionalities and the position and number of functional groups in dendrimers make them promising candidates for a wide variety of applications. In this chapter, three areas 1) hostguest chemistry 2) light harvesting and 3) drug delivery, where dendrimers are increasingly finding applications, are discussed with selected examples. Chapter 2. Hydroxyl Terminated Dendritic Oligomers from Bile Acids: Synthesis and Properties. Bile acids are excellent building blocks for dendritic construction because of their many interesting features. They are readily available, chiral, facial amphiphiles with complementary functionalities. Moreover, due to the large size of the bile acid units, a dendritic structure consisting of only a few such repeat units can have an extended structure with multiple functionalizable groups. (figure 1) The high reactivity of the chloroacetyl group has been exploited for the synthesis of bile acid based first and second-generation dendrons with glycolate linkers and multiple hydroxyl groups. The synthesis involves only a few steps and avoids the use of protecting groups for the terminal hydroxyl groups. The synthesis of a bile acid tetramer is shown here as an example (Figure 1). Carboxyl protected cholic acid was reacted with chloroacetylchloride to generate the trischloroacetylated derivative. This compound on reaction with excess of sodium cholate generated the tetramer with nine hydroxyl groups via displacement of the chlorides. In order to synthesize higher generation dendritic structures, perchloroacetylated firstgeneration dendrons were first synthesized. These were subsequently reacted with excess of sodium deoxcholate to generated secondgeneration dendrons with multiple hydroxyl groups (Figure 2). All the compounds were characterized by H NMR, C NMR, IR, ESIMS/MALDI-TOF, HPLC and elemental analysis(wherever possible) Figure 2. Structure of tridecamer. These dendritic structures with facially amphiphilic bile acid backbones on the periphery were able to solubilize cresol red, a hydrophilic dye, in a nonpolar solvent, thus exhibiting reverse micellar characteristics. Chapter 3. Multiple Naproxen Appended Bile Acid Dendrimers as Light Harvesters and Drug Carriers. Part I. Synthesis and Characterization. Using the same synthetic strategy as in Chapter 2, bile acid based dendritic structures appended with multiple bioactive (S)naproxens were generated as potential drug carriers. The construction of these dendrimers was accomplished using per(chloroacetylated) bile acid dendrons and conveniently displacing all the chlorides with naproxen units. Since naproxen is photoactive with a high fluorescence quantum Figure 3. Structures of secondgeneration dendrimers and a monomer with multiple naproxens. yield, the photophysical properties of these multichromophoric dendrimers could be further explored (Figure 3). By functionalizing the carboxyl group on the side chain with an anthracenyl moiety the energy transfer properties of these dendrimers could be studied. In this section the synthesis of first and secondgeneration dendritic structures with multiple naproxen units at the periphery and benzyl/anthracenyl moiety on the side chain are described (Figure 3). Model compounds using monomeric bile acid units were synthesized for comparison with the dendritic structures. All the compounds were characterized by H NMR, C NMR, IR, ESIMS/MALDITOF, HPLC and elemental analysis (wherever possible). Part II: Absorption, Fluorescence and Intramolelcular Energy Tranfer Studies. Absorption studies showed that the molar extinction coefficients increase linearly with increasing number of naproxen units and the absorption spectra of anthracenyl moiety remain unchanged in all the dendritic systems. These indicated the absence of ground state interaction between the chromophores. In the 275-290 nm absorption region, the molar extinction coefficient of naproxen is much greater than that of the 9-anthracenylmethyl chromophore. Hence excitation in this region would mainly excite the naphthalene chromophore. Upon excitation at 275 nm, there was predominant emission from the anthracenyl moiety in the dendritic structures (containing both chromophores) and the fluorescence intensity increased with increasing number of naproxens(Figure4). This indicated that the dendrimers act as efficient light harvesters with energy transfer from naproxen to anthracene (intramolecular nature of the energy transfer was confirmed through control experiments). (Figure 4: Refer PDF File) The fluorescence and energy-transfer properties were further investigated by time-resolved fluorescence spectroscopy. The presence of fast decay component(s) in the naproxen decay in dendritic structures (containing both chromophores) indicates that its fluorescence is quenched in the presence of anthracene due to energy transfer ((λex 275 nm, λem 350 nm (Figure 5). This was further confirmed by monitoring the fluorescence of the sensitized anthracenyl chromophore (λex 275 nm, λem 436 nm) which exhibited a fast rise comparable to he quenched naproxen lifetime(s). The efficiency of energy transfer was estimated by donor quenching by both steadystate and timeresolved techniques. The dendritic structures exhibited high energy transfer efficiencies (~ 70 – 90 %) with the net efficiency decreasing from the first to second-generation. Part III. In vitro Study of Hydrolysis of Naproxen Appended Bile Acid Prodrugs by Chemical and Enzymatic Methods. The naproxen appended bile acid dendrimers consist of hydrolyzable ester and glycolate linkers. Hence the chemical stability and enzymatic degradation with possible release of naproxen was studied. Two compounds, monomer appended with two naproxens and trimer with four naproxens have been used for the initial investigations (Figure 6). The compounds were found to be highly stable towards chemical hydrolysis and did not show any hydrolysis in phosphate buffer, pH = 7.4 even after 7 days. Since the compounds were not soluble in water, Arabic gum and TritonX were used for emulsification. Figure 6. Structures of monomer and trimer. (Refer PDF File) The enzymatic hydrolysis of the compounds was then studied using Candida Rugosa Lipase. In both cases, there was slow hydrolysis of the substrate and intermediates were formed (with release of free naproxen) which were detected by HPLC (reverse phase column with a UV detector). The trimer underwent much slower hydrolysis compared to the monomer. The intermediates were characterized by absorption and mass (ESIMSQTOF) spectrometry.

The present thesis is focused on rational design and synthesis of π-conjugated donor-acceptor (D-A) type oligomers and polymers. It is organized in six different chapters and a brief discussion on the content of the individual chapter is provided below. Chapter 1 briefly describes the charge transport properties of organic semiconductors followed by recent development of different organic semiconducting materials mainly for applications in OFET and solar cells have been highlighted. Chapter 2 explores the synthesis and characterization of two new liquid crystalline, D-A type bithiophene-benzothiazole derivatives. The liquid crystalline properties of the materials have been studied in detail with optical polarizing microscopic images and differential scanning calorimetry and found that these materials possess highly ordered smectic A liquid crystalline phase. Their charge transport properties have also been investigated by fabricating OFET devices. Chapter 3 describes the photophysical properties and OFET performance of quinoxaline based donors-acceptor-donor (D-A-D) type molecules. Depending on the flexibility and rigidity of the conjugated backbone these materials show liquid crystalline behaviour. Investigation of their OFET performance indicated that these molecules exhibit p-type mobility up to 9.7 x 10-4 cm2V-1s-1 and on/ off ratio of 104. Chapter 4 investigates excited state properties and OFET behavior of D-A-D type diketopyrrolopyrrole (DPP) derivatives end-capped with alkoxynaphthalene group. UV-Visible spectroscopy measurement shows strong intramolecular charge transfer (ICT) between donor and acceptor unit. Steady-state and time-resolved fluorescence measurements confirm the formation of excimer. The excited state interactions, the interchromophore separation and geometry of the molecules influence the extent of excimer formation. Finally, the OFET behavior of these DPP based materials has been studied using different dielectric layers. Chapter 5 discusses the synthesis, characterization and properties of two new thieno[3,2-b]thiophene-DPP based donor-acceptor (D-A) type low band gap polymers (PTTDPP-BDT and PTTDPP-BZT). Investigation of OFET performance indicated that polymers exhibited ambipolar behaviour with hole mobility upto 1.0 x 10-3 cm2/Vs and electron mobility upto 8 x 10-5 cm2/Vs. Using polymer PTTDPP-BDT with electron acceptor C70PCBM, power conversion efficiency (PCE) around 3.26% in bulk heterojunction solar cell has been achieved. Chapter 6 describes the approach to tailor the energy levels of conjugated polymers (PTDPP-IDT and PTTDPP-IDT) based on Indacenodithiophene (IDT) coupled with DPP moieties. We have studied the photovoltaic performance of these conjugated polymers by blending with PCBM and P3HT. The importance of these materials in polymer/polymer blend solar cell has been emphasized. The photovoltaic devices with polymer/polymer blend solar cell exhibit high open-circuit voltages (VOC) of ~ 0.8 V. In summary, the work presented in this thesis describes synthesis, characterization and photophysical properties of new organic semiconductors and their importance in optoelectronic devices. This work also describes a general design principle of nonfullerene organic solar cell. The results described here show that these materials have potential application as active components in plastic electronics.