This work examines various light metal borohydrides, particularly those formed from group II metals, with the aim of understanding their fundamental physical properties and improving their hydrogen storage ability. The structure of a new phase (γ) of Mg(BH₄)₂ is reported and the decomposition is fully characterized in a combination of diffraction and thermogravimetric studies. The bulk properties of γ-Mg(BH₄)₂ are compared to those of an SiO₂ isostructure and probed by various neutron scattering techniques. Negative thermal expansion is observed at low temperatures and the material absorbs up to 1.5 moles of hydrogen gas to form one of the most gravimetrically hydrogen-dense materials ever reported. The structural evolution of Ca(BH₄)₂ under different synthetic conditions and external influences (e.g. temperature) is studied up until the material decomposes. The effects of various additives on group II metal borohydrides are also examined and the influence of each is justified by observing subtle structural changes in the mixed system via in situ synchrotron X-ray powder diffraction and ¹¹B NMR measurements.

The work described in this thesis involves the study of weak interactions by NMR spectroscopy and using them to develop novel applications. The two different applications chosen are i) using molecular interactions for chiral discrimination and ii) understanding the nature of the interaction between peptide and nanoparticles to develop potent antibacterial agents. The thesis, which is divided into five chapters starts with a general introduction of NMR spectroscopy for the study of molecular interactions in conjunction with other techniques. The remaining four chapters focus on four different areas/projects that I have worked on. Chapter 1: Introduction This chapter reviews different kinds of molecular interactions along with the introduction to NMR spectroscopy and other techniques used for all the studies. Starting with the application of chiral discrimination the chapter proceeds to the general introduction of antimicrobial peptides, silver nanoparticles and the strategy for peptide resonance assignment. Chapter 2: Chiral discrimination for versatile functionalities There are many chiral agents available for discriminating enantiomers which mainly target specific functional groups. In this study, we have explored a strategy involving ternary complexation to investigate chiral discrimination of different kind of functional groups by NMR spectroscopy. The proposed protocol was employed for the enantiodiscrimination of molecules containing functional groups, such as amino alcohols, secondary alcohols, cyanohydrins, oxazolidones, diols, thiones and epoxides, using a phosphorous based three component mixture. The simple mixing and shaking of enantiopure 1,1’-binaphthyl-2,2’-diyl hydrogenphosphate (BNPA), 4-(dimethylamino)pyridine (DMAP) and a chiral analyte in the solvent CDCl3 served as a chiral solvating agent and resulted in well-dispersed peaks for each enantiomer in the 1H NMR spectrum. Discrimination was achieved not only for the proton at the chiral center but also for multiple proton sites. The J-resolved technique was used for alleviating the spectral complexity pattern to accurately measure the chemical shift difference. The devised approach also permitted the precise measurement of the enantiomeric excess (ee). Chapter 3: Simultaneous discrimination of secondary alcohols and carboxylic acids In this chapter, I describe two novel ternary ion-pair complexes, which serve as chiral solvating agents (CSA), for enantio discrimination of secondary alcohols and carboxylic acids. The superiority of CSA over other auxiliaries arises due to the formation of diastereomeric complexes through non-covalent interactions with the analyte. By exploiting the acid-base interaction strategy and employing DMAP, which further enhanced the hydrogen bonding efficiency the discrimination for both carboxylic acids and secondary alcohols were achieved. The protocol for discrimination of secondary alcohols is designed by using one equivalent mixture each of enantiopure mandelic acid, 4-dimethylaminopyridine (DMAP) and a chiral alcohol. For discrimination of carboxylic acids, the ternary complex is obtained by one equivalent mixture each of enantiopure chiral alcohol, DMAP, and a carboxylic acid. Furthermore, the formation of the complex was supported by calculating the energy-minimized structure of the proposed complex by density functional theory (DFT). The designed protocols also permit accurate measurement of the enantiomeric composition. Chapter 4: Enhanced potency of nanoparticle-antimicrobial peptide conjugates Antibiotic resistance is emerging as the new global health problem. Due to the blatant misuse and overuse of these drugs has resulted in the bacteria becoming resistant to a wide range of antibiotics. Researchers have found an alternative of current antibiotics which are a group of peptides known as antimicrobial peptides (AMP). But using these molecules as drug is rather costly due to high synthesis cost. Further the antibacterial activity of silver nanoparticle is well established. However, due to its toxic nature after, it cannot be used in high concentration. The conjugation of nanoparticles with antimicrobial peptides is emerging as a promising route to achieve superior anti-microbial activity. However, the nature of peptide-nanoparticle interactions in these systems remains unclear. This study describes the interactions of antimicrobial peptide with silver nanoparticles by NMR spectroscopy in conjunction with other biophysical techniques to completely understand the underlying mechanism of interaction between nanoparticles and peptide. It reveals that the conjugation process involves dynamic interaction between the nanoparticle and the peptide. This study also confirms the enhanced antibacterial efficiency of the nano-conjugate towards bacterial killing compared to the nanoparticle or the peptide alone. Chapter 5: Mechanistic insights into the action of nano-conjugates It is well established that antimicrobial peptides act as pore-formers to rupture the bacterial cells. This chapter is focused on studying the mechanism of action of the nano-conjugate with bacterial membrane mimic models. This study for the first time reveals the details of nanoconjugate membrane interaction at an atomic level. The pore formation mechanism and the enhanced efficiency of the nanoconjugate were explored using fluorescence spectroscopy, CD spectroscopy, and NMR spectroscopy. Structural changes of the peptide and the nanoparticle bound peptide have been captured which infers the propensity of the peptide to form a helical structure upon interacting with the membrane. The calculated structure of the peptide and nanoparticle bound peptide remains almost identical in presence of the membrane mimic environment. In the case of the nanoconjugate, the increase in local positive charge concentration makes the system to penetrate the bacterial membrane faster which further allows the nanoparticle to access the intercellular organelles easily. This dual mode of mechanism thus makes this nano-conjugate a promising antibacterial agent towards multi drug resistant bacteria. In summary, the thesis has focused on the studies of weak intermolecular interactions in different chemical and biological systems using NMR spectroscopy. It is demonstrated that in certain chemical systems, such interactions can be exploited to discriminate enantiomers and determine the enantiopurity of compounds by NMR. In the case of biomolecules, such weak interactions exist when protein or peptides interact with nanoparticles. Using silver nanoparticles, it is shown that such interactions result in a stable conjugate system. NMR spectroscopy provides valuable insights into the structure and dynamics of the system. Further, by using anti-microbial peptides conjugated with silver nanoparticles, new superior antibacterial agents can be developed.

The thesis entitled “Unravelling the Nature of Halogen and Chalcogen Intermolecular Interactions by Charge Density Analysis" consists of five chapters. A basic introductory section describes the topics relevant to the work and the methods and techniques utilized. The main focus of the present work is to characterize the interaction patterns devoid of strong classical hydrogen bonds. The case studies include halogen bonds and hydrogen bonds involving bromine (as a halogen bond donor and hydrogen bond acceptor), intermolecular chalcogen bond formation involving sulphur, type I Br Br contacts, type II F F and F S interactions and S-H S hydrogen bonds. Chapter 1 discusses experimental and theoretical charge density analyses on 2,2-dibromo-2,3-dihydroinden-1-one which has been carried out to quantify the topological features of a short C Br···O halogen bond with nearly linear geometry (2.922Å, C Br···O=172.7) and to assess the strength of the interactions using the topological features of the electron density. The electrostatic potential map indicates the presence of the “- hole” on bromine while the interaction energy is comparable to that of a moderate O-H O hydrogen bond. In addition, the energetic contribution of C-H···Br interaction is demonstrated to be on par with that of the C-Br···O halogen bond in stabilizing the crystal structure. Chapter 2 discusses an organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole that has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystall zing in a non-centrosymmetric space group (Z =1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (=2). Topological analysis based on QTAIM clearly brings out the dominance of chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms. Chapter 3 discusses the role of a type I C-Br Br-C contact and what drives the contact i.e. how a dispersive interaction is stabilized by the remaining contacts in the structure. In the process we observe the role the Br2Cl motif which is quite unique in its nature. Also the role of the bromine atoms in stabilizing the stacking interactions has been shown by the electrostatic potentials which are oriented perpendicular to the plane of the benzene ring. Chapter 4 discusses the enigmatic type II C-F F-C and C-FS-C interactions in pentafluorophenyl 2,2- bithiazole. Both the interactions are shown to be realistic “-hole” interactions based on high resolution X-ray charge density analysis. As fluorine is the most electronegative element, its participation in halogen bonding wherein the electrostatic potential around the atom gets redistributed to form regions of electron depletion and accumulation had time and again been speculated but never observed. In this chapter the experimental charge dnsity analysis clearly identifies the “-hole” on fluorine and distinguishes the C-F S-C interaction as a halogen bond rather than the chalcogen bond. Chapter 5 discusses the experimental charge density analysis of the hitherto unexplored S-H S hydrogen bond in crystal structures. The work highlights how relatively small is the number of crystal structures which are constructed by the S-H S hydrogen bond compared to the X-H S hydrogen bond via Cambridge Structural Database (CSD) analysis. The potential S-H S hydrogen bond is studied in three isomeric mercaptobenzoic acids with experimental charge density collected on 2-mercaptobenzoic acid and theoretical estimates made on 3- and 4-mercaptobenzoic acid. The strength and directionality of the S-H S hydrogen bond is demonstrated to be mainly due to the conformation locking potential of intramolecular S O halogen bond.

This Thesis explores the role of structural defects and disorder and their relationship to experimental data, with a particular emphasis on molecular framework materials. The question of how we can build atomistic models of amorphous materials from experimental data without needing to make system-specific assumptions is addressed. The role of 'structural invariance', <i>i.e.</i> the limited range of distinct local atomic environments within a material, as a restraint within reverse Monte Carlo refinement (RMC) is investigated. The operation of these invariance restraints operate is shown to be system-dependent and the challenges associated with effective refinement, <i>e.g.</i> configurational 'jamming', are also investigated. A generalisation to the 'structural simplicity', <i>i.e.</i> the simplest model, holding all else constant, is most likely to be correct. Three new metrics of structural simplicity are proposed: two intrinsically three-dimensional measures of local geometric invariance and one measure of local symmetry. These metrics are shown to robustly quantify the configurational quality. The ability of these metrics to act as effective restraints for the RMC refinement of amorphous materials is demonstrated by the construction of the first data-driven tetrahedral models of amorphous silicon. The role of defects and disorder within metal–organic frameworks (MOFs) is investigated through the canonical MOF UiO-66(Hf). Through a combination of techniques, including X-ray diffuse scattering, anomalous diffraction, total scattering and electron diffraction measurements, the existence of correlated metal-cluster absences in UiO-66(Hf) is demonstrated. Furthermore the ability to synthetically tune both the interactions and concentration of defects is shown. The thermomechanical properties of defective UiO-66(Hf) are also examined. UiO-66(Hf) is shown to rapidly densify by up to 5% (ΔV/V ) on ligand elimination. The resultant densified phase exhibits colossal (≥100MK^-1) volumetric negative thermal expansion (NTE); the largest reported value for any MOF. Finally, the capability to tune the physical properties of MOFs through defect incorporation is demonstrated through the defect-dependence of both the densification and the NTE.

Crystal engineering offers a rational way of analyzing crystal structures and designing new structures with properties. The supramolecular synthon concept was introduced in 1995 and has shown versatility and utility in the design of molecular solids. Chapter 1 gives a general introduction about the development of the concept of supramolecular synthons over the years which has seen a transition from synthesis to structures and dynamics. This thesis focuses on the later phase of the development of the concept of supramolecular synthons. Chapter 2 introduces the idea of structural landscape and describes a structural landscape of a conformationally flexible molecule, orcinol, and explores the synthon preferences of this particular molecule towards cocrystal formation. Chapter 3 explores a combinatorial matrix to show both global and local features of a structural landscape. Chapter 4 takes a component of this landscape namely 4,4'-bipyridine and 4-hydroxybenzoic acid and shows the occurrence of synthon polymorphism in cocrystals which originates from the interplay of geometrical and chemical factors. Chapter 5 introduces a four step method for the identification of multiple synthons by FTIR spectroscopy. Along with, it shows that the rarity of synthon polymorphism is not a case of overlooking of crystals in the process of selecting good looking crystals. Chapter 6 takes a series of dihalogenated phenols and indicates that the Br prefers type II. This chapter also explains elastic bending on the basis of halogen bonds. Chapter 7 attempts to explore the Cl/Br isostructurality in the light of type I and type II contacts and concludes that Cl/Br isostructurality arises from a geometrical model and therefore it is quite similar to Cl/Me isostructurality. Chapter 8 attempts to analyze the class of trichlorophenols and reveals structural modularity in this class of compounds. The modularity of 3,4,5-trichlorophenol is explored in crystal design in chapter 9 in terms of LSAM (Long Range Synthon Aufbau Module) A subsequent study in solution by NMR reveals the presence of LSAM in solution and establishes a hierarchy of the dissociation of its components. The concept of supramolecular synthon has come a long way from being a tool in a crystal engineer’s toolbox to a structural unit responsible for crystallization and therefore offer multiple possibilities both in terms of structures and dynamics. This thesis attempts to explore some of these possibilities based mainly on the concepts of structural landscape and halogen bonds which are blended with the concept of supramolecular synthons.

Materials chemistry basically deals with rational design and synthesis of new solids exhibiting various functional properties. A sound knowledge of crystal structures and chemical bonding is needed to understand the properties of materials. Space group, cell parameters and atomic positions provide a basic crystallographic description of the structure. Crystal structure could be described in a detailed way in terms of close packing of anions and occupancy of cations in different coordination sites. The coordination polyhedra and their interconnectivity bring out the interrelationships between different structures and the properties exhibited. Transition metals (TMs) are d-block elements which occupy groups 3-12 in Periodic Table. IUPAC defines a TM as ‘an element whose atoms have partially filled d-shell, or which can give rise to cations with an incomplete d-shell’. The partially filled d-shell in TMs plays an important role in various chemical and physical properties of TMs. Although TM cations can form compounds with different anions, most of the TM containing compounds are metal oxides due to the large free energies for formation of oxides. Binary TM oxides adopt different kinds of structures among which rock salt (e.g. NiO), rutile (e.g. TiO2), and corundum (e.g. Cr2O3) are most common. Ternary TM oxides are also known to form in variety of structures with the perovskite (e.g. BaTiO3), and the spinel (e.g. MgFe2O4) structures being well known. TM oxides exhibit a broad range of electronic and magnetic properties. TM oxides, at one end, display metallic behavior (e.g. ReO3, RuO2, LaNiO3) due to the delocalized electrons and at other end, show insulating behavior (e.g. NiO) due to the localized electrons. In between, TM oxides have semiconducting properties involving either the hopping of carriers (e.g. partially reduced TiO2, Nb2O5, WO3 and so on) or the electron excitation from the valence band to the conduction band (e.g. SnO2). TM oxides are known to have diverse magnetic properties: diamagnetic (e.g. TiO2, ZrO2), paramagnetic (e.g. VO2, NbO2), ferromagnetic (e.g. CrO2, La0.67Ca0.33MnO3), ferrimagnetic (e.g. Fe3O4, MnFe2O4) and antiferromagnetic (e.g. NiO, LaCrO3). TM oxides with partially filled 3d-shell are expected to be ‘metallic’ according to Bloch-Wilson theory, but in practice they are Mott insulators (localized 3d electrons) because of correlation energy (U) involved in the transfer of d-electrons between adjacent sites. Certain TM oxides also show insulator-metal (I-M) transitions induced by change of temperature, pressure or composition. For example, VO2 and Ba2IrO4 are known for their temperature and pressure induced I-M transitions, respectively. La1-xSrxCoO3 becomes metal at a particular Sr concentration being one of the examples for composition-dependent I-M transition. TM oxides are usually synthesized by conventional ceramic method in which stoichiometric mixture of starting materials is reacted at elevated temperatures. Multiple prolonged heating with intermittent grindings in ceramic method generally results in thermodynamically controlled products. The metastable phases which are of interest may not be obtained by ceramic method. Chimie douce/soft chemistry methods are generally adopted to stabilize the metastable phases. The guiding principle behind the chimie douce is to have kinetic control (rather than thermodynamic control) to realize metastable phases. Accordingly, metastable derivatives are obtained by choosing appropriate precursors, or adopting sol-gel and molten flux or ion exchange/intercalation methods. The present thesis is devoted to an investigation of transition metal oxides towards development of functional materials exhibiting visible light absorption/emission and lithium insertion/extraction for cathode materials in lithium ion battery. TM oxides find application as photovoltaic materials, luminescent emission materials, photocatalysts, light absorption/pigment materials and so on, based on their optical properties. Ferroelectric TM oxides with perovskite structure [Green coloured (KNbO3)1-x (BaNi1/2Nb1/2O3-δ)x] are studied currently as photovoltaic materials which show high open circuit voltage (Voc = 3.5 V) despite very low short circuit current (Vsc = 40 nA cm-2). TM oxides are also known to exhibit photoluminescent emission which could be due to the doping activator ions (e.g. MnII doped Zn2GeO4) or TM oxide (e.g. CaWO4) itself being self-activator. While the green and red emissions are common for TM oxides, blue emission is rare (e.g. Ar+ irradiated SrTiO3 is a blue emitter). Coloured TM oxides with band gap in visible region are employed as photocatalysts for solar water splitting (e.g. yellow BiVO4, yellow Ag3PO4, yellow TaON, red Fe2O3) and photo-oxidation of organic pollutants (e.g. TiO2-xNx and CaCu3Ti4O12). The coloured TM oxides also find application as pigments from early times, for example, Egyptian blue (CaCuSi4O10), Han blue (BaCuSi4O10), Han purple (BaCuSi2O6), Malachite green (Cu2CO3(OH)2), Ochre red (Fe2O3) and many others. A list of pigments based on TM oxides is given in Table 1. Pigment materials are applied as colouring materials in inks, dyes, paints, plastics, ceramics glazers, enamels and textiles. Table 1. List of TM oxide based pigments and their colours Pigment colour Compound White Titanium dioxide (TiO2) Black Iron oxide black (Fe3O4) Red Iron oxide red (Fe2O3), Ca1-xLaxTaO2-xN1+x (yellow-red) Orange Iron oxide orange (Fe2O3) Yellow Yellow ochre [FeO(OH)·H2O] Green Malachite green [Cu2CO3(OH)2], Viridian (Cr2O3. 2H2O), Y2BaCuO5 Blue Egyptian blue (CaCuSi4O10),Cobalt aluminate (CoAl2O4), YIn1-xMnxO3 Purple Han purple (BaCuSi2O6) Violet Cobalt phosphate [Co3(PO4)2] Colours of the TM oxides arise from visible light absorption due to the ligand field d-d electronic transitions. Though d-d transitions are parity forbidden, the selection rules get relaxed due to different reasons such as symmetry reduction (due to distortion) and vibronic couplings. The colour of the TM oxides is influenced mainly by two factors (i) oxidation state of TM ion present and (ii) ligand field around the TM ion produced by anion geometry. In order to develop new pigment oxides, our strategy was to choose colourless metal oxides having unusual (five coordinated geometry) or irregular/distorted (distorted octahedral/tetrahedral) coordination geometries around metal ion and produce coloured oxides by substituting 3d-TM ions at the metal ion site. We made a detailed study on the origin of the colour and pigment quality of the resulting coloured oxides. In the present thesis, which has two parts, the first part (Part 1) discusses the development of 3d-TM ion substituted coloured oxides with potential for pigment applications. Chapter 1.1 describes the purple inorganic pigment, YGa1-xMnxO3 (0 < x ≤ 0.10), based on the hexagonal YGaO3. The metastable series of oxides were prepared by a sol-gel technique where the dried gels, obtained from aqueous solutions of metal nitrates-citric acid mixtures, were calcined for a short duration in preheated furnace around 850°C/10 mins. The purple colour of the oxides arises from the specific trigonal bipyramidal ligand field around MnIII that obtains in the YGaO3 host. Other hexagonal RGaO3 hosts for R = Lu, Tm and Ho substituted with MnIII also produce similar purple coloured materials. In Chapter 1.2, we present a study on substitution of 3d-TM ions in LiMgBO3 host [where Mg(II) has a trigonal bipyramidal (TBP) oxygen coordination)]. We find that single-phase materials are formed for LiMg1-xCo(II)xBO3 (0 < x ≤ 1.0), LiMg1-xNi(II)xBO3 (0 < x ≤ 0.1), LiMg1-xCu(II)xBO3 (0 < x ≤ 0.1) and also Li1-xMg1-xFe(III)xBO3 (0 < x ≤ 0.1) of which the Co(II) and Ni(II) derivatives are strongly coloured, purple-blue and beige-red respectively, thus identifying TBP CoO5 and NiO5 as the new chromophores for these colours. Chapter 1.3 describes the synthesis, crystal structures and optical absorption spectra/colours of 3d-TM substituted α-LiZnBO3 derivatives: α-LiZn1-xMIIxBO3 [MII = CoII (0 < x < 0.50), NiII (0 < x ≤ 0.05) and CuII (0 < x 0.10)] and α-Li1+xZn1-2xMIIIxBO3 [MIII = MnIII (0 < x ≤ 0.10) and FeIII (0 < x 0.25)]. The crystal structure of the host α-LiZnBO3, which is both disordered and distorted with respect to Li and Zn occupancies and coordination geometries, is largely retained in the derivatives, giving rise to unique colours [blue for CoII, magenta for NiII and violet for CuII], that could be of significance for the development of new, inexpensive and environmentally-benevolent pigment materials, especially for the blue colour. Accordingly, the work indentifies distorted tetrahedral MO4 (M = Co, Ni, Cu) (together with a long M-O bond that gives a trigonal bipyramidal geometry) structural units as the new chromophores for the blue, magenta and violet colours respectively, in the α-LiZnBO3 host. In Chapter 1.4, we describe the synthesis, crystal structures and optical absorption spectra of 3d-TM substituted spiroffite derivatives, Zn2-xMxTe3O8 (MII = Co, Ni, Cu; 0 < x ≤ 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620°C/12h. Rietveld refinement of the crystal structures from powder XRD data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/MII – O bonds (1.898 – 2.236 Å) and one longer Zn/MII– O bond (2.356 – 2.519 Å). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/MII – O chromophores. We could not however prepare the fully-substituted M2Te3O8 (MII = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions. Red coloured materials are rare in nature. Li2MnO3 is a unique oxide with an unusual red colour imparted by MnIV ions. Chapter 1.5 describes a detailed experimental investigation of Li2MnO3 together with other related MnIV oxides that probes the red colour of Li2MnO3 as well as its photoluminescence. Optical absorption spectra reveal a strong band gap absorption with a sharp edge at ~ 610 nm and a transparent region between ~ 610 and ~ 650 nm that causes the red colour of Li2MnO3 samples. Octahedral MnIV ligand field transitions, corresponding to both MnIV at ideal sites and MnIV displaced to Li sites in the rock salt based layered structure of Li2MnO3, are observed in the excitation spectra of Li2MnO3 samples. Optical excitation at the ligand field transition energies produces tunable emission in the red-yellow-green region, rendering Li2MnO3 a unique MnIV oxide. The honeycomb ordered [LiMn6] units in the structure likely causes both the absorption and photoluminescence properties of Li2MnO3. Lithium containing TM oxides with rock salt related structure are being investigated extensively for application as next generation cathode materials for Lithium ion batteries (LIBs). Recent research is focused on lithium-rich layered oxides (LLOs) which are solid solutions between Li2MO3 (where M = Ti, Mn and Ru) and LiMO2 (where M = Cr, Mn, Fe, Co, Ni). LLOs have excess lithium in the TM layer in addition to lithium in lithium layer of rock salt derived structure. LLOs have gained attention because of their higher discharge capacity in the range of ~ 250 mAhg-1. While most of the LLOs investigated so far contain 3d-TM ions (Mn, Fe, Co, Ni), recently there has been an interest in the study of the role of ruthenium in addition to 3d-TM ions. We have investigated ruthenium containing LLOs with a view to probe (i) the role of ruthenium and (ii) the concentration of excess lithium in the TM layers in producing higher discharge capacities. The results are discussed in the Part 2 of the thesis.Li5NiMnRuO8(Li[Li0.25Ni0.25Mn0.25Ru0.25]O2) form in the Li2RuO3 crystal structure. Electrochemical studies indicate that the Co-containing oxides exhibit a higher initial discharge capacity (for e.g. ~ 180 mAhg-1 for Li4CoRuO6) as well as a higher reversible discharge capacity (~130 mAhg-1 for Li4CoRuO6) compared to the corresponding Ni-analogs. Participation of oxide ions (higher oxidation state of Ru) in the redox process could explain the higher discharge capacity during the first cycle. Reduced capacity (capacity fade) during the subsequent cycles could arise from the oxygen evolution due to the redox process (2O2- → 2O- → O2), which is not reversible. The present work shows that ruthenium incorporation in rock salt layered oxides along with Co/Ni appears to give a beneficial effect in producing a higher discharge capacity. In addition, the compounds crystallizing with the R-3m structure (related to LiCoO2) appear to give a better reversible capacity than the compounds crystallizing in the C2/c structures (Li2TiO3 and Li2RuO3).

The development of a clean hydrogen economy will aid a smooth transition from fossil fuels which is required to stem the environmental impact and economic instability caused by oil dependency. For vehicular application, in addition to being cheap and safe, a commercial hydrogen store must contain a certain weight percentage of hydrogen to provide a reasonable range (~300 miles). It must also be able to release hydrogen under near-ambient conditions (80-120°C) and have a reasonable cycling capacity (~1000 cycles). The primary motivation of this thesis is to gain a fundamental understanding into the sorption processes of hydrogen on carbon- and aluminium-based materials to improve their hydrogen storage capacity. The sorption processes of hydrogen on mechanically milled graphite have been investigated, primarily using Electron Spin Resonance Spectroscopy and Inelastic Neutron Scattering. An investigation into the storage properties of tetrahydroaluminates, primarily NaAlH₄ and LiAlH₄, is performed in the presence and absence of a catalyst, and a new phase of NaAlH₄ is observed prior to its decomposition. Variable temperature neutron and synchrotron diffraction, in conjunction with gravimetric and mass spectroscopy data were obtained for several mixtures of tetrahydroaluminates and alkali amides and the hydrogen desorption processes are shown to be quite different from the constituent materials. The structure of Ca(AlH₄)₂ has been experimentally determined for the first time and a complete set of equations describing its decomposition pathway is given.

The thesis entitled “Structure-function control in organic co-crystals/salts via studies on polymorphism, phase transitions and stoichiometric variants” consists of five chapters. The main emphasis of the thesis is on two aspects, one to characterize co-crystal polymorphism in terms of propensity of intermolecular interactions to form co-crystals/salts or eutectics. The other aspect is to explore the feasibility of using such co-crystals/salts to exhibit properties like proton conduction, dielectric and ferroelectric behaviour. Gallic acid and its analogues possess functionalities to provide extensive hydrogen bonding capabilities and are chosen as the main component while the coformers are carefully selected such that they either accept or reject the hydrogen bonding offered. Such co-crystallization experiments therefore provide an opportunity to unravel the intricate details of the formation of crystalline polymorphs and/or eutectics at the molecular level. Further these co-crystal systems have been exploited to evaluate proton conductivity, dielectric and ferroelectric features since the focus is also on the design aspect of functional materials. In the context of identifying and utilizing Crystal Engineering tools, the discussions in the following chapters address not only the structural details but identify the required patterns and motifs to enable the design of multi-component co-crystals/salts and eutectics. In particular, the presence/absence of lattice water in gallic acid has been evaluated in terms of importing the required physical property to the system. Chapter 1 discusses the structural features of tetramorphic anhydrous co-crystals (1:1; which are synthon polymorphs) generated from a methanolic solution of gallic acid monohydrate and acetamide, all of which convert to a stable form on complete drying. The pathway to the stable form (1:3 co-crystal) is explained based on the variability in the hydrogen bonding patterns followed by lattice energy calculations. Chapter 2A studies the presence/absence and geometric disposition of hydroxyl functionality on hydroxybenzoic acids to drive the formation of co-crystal/eutectic in imide-carboxylic acid combinations. In Chapter 2B the crystal form diversity of gallic acid-succinimide co-crystals are evaluated with major implications towards the design and control of targeted multi-component crystal forms. The co-crystal obtained in this study shows a rare phenomenon of concomitant solvation besides concomitant polymorphism and thus making it difficult to obtain a phase-pure crystal form in bulk quantity. This issue has been resolved and formation of desired target solid form is demonstrated. Thus, this study addresses the nemesis issues of co-crystallization with implications in comprehending the kinetics and thermodynamics of the phenomenon in the goal of making desired materials. Chapter 3 focuses on the systematic co-crystallization of hydroxybenzoic acids with hexamine using liquid assisted grinding (LAG) which show facile solid state interconversion among different stoichiometric variants. The reversible interconversion brought about by varying both the acid and base components in tandem is shown to be a consequence of hydrogen bonded synthon modularity present in the crystal structures analyzed in this context. In Chapter 4A, the rationale for the proton conduction in hydrated/anhydrous salt/co-crystal of gallic acid - isoniazid is provided in terms of the structural characteristics and the conduction pathway is identified to follow Grotthuss like mechanism which is supplemented by theoretical calculations. Chapter 4B describes an extensive examination of the hydrated salt of gallic acid-isoniazid which unravels the irreversible nature of the dielectric property upon dehydration and suggests that the “ferroelectric like” behaviour is indeed not authenticated. This chapter brings out the significance role of lattice water in controlling the resulting physical property (dielectric/ferroelectric in this case). Chapter 5 describes the structural features of two hydrated quaternary salts of hydroxybenzoic acids-isoniazid-sulfuric acid and the phase transitions at both low and high temperatures are shown to be reversible. Single Crystal to Single Crystal (SCSC) in situ measurement corroborated by thermal and in situ Powder X-ray Diffraction studies proves the claim. Further, the properties exhibited by these materials are also governed by lattice water content.

The thesis entitled “Addressing subtle physicochemical features exhibited by molecular crystals via Experimental and Theoretical Charge Density Analysis” consists of five chapters. An introductory note provides a brief description of experimental and theoretical charge density methodology, followed by its utilization in obtaining certain physical and chemical properties in molecular crystals. Chapter 1 addresses not so easily accessed molecular property arising due to electron conjugation, highlighting antiaromaticity in tetracyclones. A systematic study of six tetracyclone derivatives with electron withdrawing and electron donating substituents has been carried out using experimental and theoretical charge density analysis. A three pronged approach based on quantum theory of atoms in molecules (QTAIM), nucleus independent chemical shifts (NICS), and source function (SF) has been employed to establish the degree of antiaromaticity of the central five-membered ring in all the derivatives. Electrostatic potentials mapped on the is density surface reveal the finer effects of different electron withdrawing and electron donating substituents on the carbonyl group. Chapter 2 presents a temperature induced reversible first order single crystal to single crystal phase transition (Room temperature Orthorhombic, P22121 to low temperature Monoclinic, P21) in a  hybrid peptide, Boc-γ4(R)Val-Val-OH. The thermal behavior accompanying the phase transition of the dipeptide crystal was characterized by differential scanning calorimetry, visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. The reversible nature of the phase transition is traced to be due to an interplay between enthalpy and entropy. Chapter 3 brings out an unusual stabilizing interaction involving a cooperative -hole and ¬hole character in a short NCS···NCS bond. This chapter describes structural features of four isothiocyanate derivatives, FmocXCH2NCS; X=Leu, Ile, Val and Ala. Among these it is observed that only FmocLeuCH2NCS which crystallizes in a tetragonal space group, P41, (a=b=12.4405(5) Å; c= 13.4141(8) Å) transforms isomorphously to a low temperature form, P41, (a=b=17.4665(1) Å; c= 13.1291(1) Å). The characteristics of the phase transition have been monitored by Differential Scanning Calorimetry, variable temperature IR and temperature dependent unit cell measurements. The short NCS···NCS intermolecular interaction (3.296(1) Å) is analyzed based on detailed experimental charge density analysis which reveals the nature of this stabilizing interaction. Chapter 4 explains a comparative study of syn and anti conformations of carboxylic acids in peptides from both structural aspect and charge density features. Single crystal structures of four peptides having syn conformations [BocLeuγ4(R)Valγ4(R)ValOH, BocLeuγ4(R)ValLeuγ4(R)ValOH, Boc3(S)Leu3(S)LeuOH] and one with anti conformation, BocLeuγ4(R)ValValOH have been analyzed. Experimental charge density analysis has been carried out exclusively on BocLeuγ4(R)ValValOH having anti form, because of its rare occurrence in literature. However, low temperature datasets on the four peptides with syn conformations were collected and theoretical charge density analysis has been carried out on two of these compounds. Electrostatic potentials mapped on is density surface bring out a significant difference at the oxygen atoms of the carboxyl group in the two conformations. However, lone pair orientation of different types of Oxygen atoms in the two forms (urethane, amide, acid) doesn’t exclusively indicate the differences in the corresponding charge density features. Chapter 5 addresses the issue of how sensitive are the charge density features associated with amino acid residues when the backbone conformational angles are varied. Three model systems, 1, L-alanyl–L-alanyl–L-alanine dehydrate; 2, anhydrous L-alanyl–L-alanyl–L¬alanine and 3, cyclo-(D,L-Pro)2(L-Ala)4 monohydrate have been chosen for this evaluation. Compound 1 has ant parallel alignment of tripe tide strands, and compound 2 has parallel alignment. All the alanine residues in compound 1 and 2 are in the -sheet region of the Ramachandran plot, whereas, the four Alanine residues in the cyclic hex peptide 3 span different regions of the Ramachandran plot. Theoretical multipole modelling has been carried out in order to explore the plausibility of transferring multipole parameters across different regions of Ramachandran Plot. Appendix I contains a brief description of charge shift bonding in Ph-CH2-Se-Se-CH2-Ph, as determined based on both experimental and theoretical charge density analysis. Appendix II contains a reprint of a published article on “Conformation-Changing Aggregation in Hydroxyacetone: A Combined Low-Temperature FTIR, Jet, and Crystallographic Study”.

Maleimide based highly luminescent material Cbz-MI with donor acceptor donor (D-A-D) backbone has been synthesized and characterized. An organic light emitting diode fabricated using this material as emitting layer exhibited EQE of 2.5% in the yellow region of visible spectrum. Due to the small energy gap of materials emitting in this region of spectrum, EQE of OLED is usually limited by various non-radiative decays and high EQE of OLED using this material proves that most of the nonradiative decay pathways have been avoided by the careful design of molecule and device structure. Although Cbz-MI did not show TADF properties, but if tailored with right electron donor along with maleimide as an acceptor, such derivatives may exhibit TADF properties