In molecular magnetism, rational design and serendipity have played complementary roles in the synthesis of complexes which display a breadth of interesting physical characteristics. These range from the basic understanding of magneto‐structural correlations, to more complicated phenomena such as slow relaxation of the magnetisation, spin frustration effects, and tuning magnetic interactions with a view to spintronics. The inherent physical properties of these complexes has already afforded molecules which can behave as single‐molecule magnets, singlechain magnets, single‐ion magnets, magnetic metal‐organic frameworks, magnetic refrigerants, and molecular qubits. Even when the building blocks are well known, the rational design of magnetic clusters can be extremely difficult, with the shape and nuclearity often dominated by several internal and external factors. Metallosupramolecular processes proffer an attractive strategy to the rational design of these clusters by making use of structurally‐rigid precursors which, when combined in the correct stoichiometric ratio, can be used to construct various predefined discrete two‐ and three‐dimensional polygons and polyhedra. In particular, the use of metalloligands as structurally‐rigid precursors is appealing, not only because of their often‐straightforward synthesis, but because of their ability to be easily modified in order to create comparable building blocks with different chemical and physical properties. It is therefore surprising that there are limited examples of magnetic architectures built through this approach. Each chapter of this thesis aims to exploit the use of acetylacetonate‐based paramagnetic metalloligands for the synthesis of structurally analogous magnetic coordination capsules, with inherently different magnetic properties. Chapter 2 describes the structural and magnetic studies of fourteen tetradecanuclear coordination cubes, synthesised using the paramagnetic metalloligand [MIIIL3] (MIII = Cr, Fe; HL = 1‐(4‐pyridyl)butane‐1,3‐dione). The heterometallic [MIII8MII6L24]n+ (MII = Co, Ni, Cu, and Pd; n = 0‐ 12) cubes formed from the reaction of [MIIIL3] and a “naked” MII salt are all topologically similar, with the MIII ions occupying the corners of the cubes and the MII ions occupying the faces. Excluding the PdII‐based cube, all of the complexes display magnetic exchange interactions at low temperatures. Due to the enormous size of these clusters and their resulting matrices, the magnetic fitting was done using the process of statistical spectroscopy. Chapter 3 describes the structural and magnetic studies of five [MIII2MII3L6]n+ (MIII = Cr, Fe, and Al; MII = Co, Zn, and Pd; HL = 1‐(4‐pyridyl)butane‐1,3‐dione; n = 0‐6) trigonal bipyramids, built using the diamagnetic and paramagnetic metalloligands [MIIIL3]. [FeIII2CoII3L6Cl6] represents the first magnetic trigonal bipyramid synthesised through the pyridyl‐based metalloligand approach. SQUID magnetometry studies show a weak antiferromagnetic exchange interactions between the FeIII and CoII ions, while EPR spectroscopy measurements demonstrate a small increase in the zero‐field splitting parameter of the FeIII ion upon coordination of [FeIIIL3] to a MII ion. Complete active space self‐consistent field (CASSCF) calculations show the axial zero‐field splitting parameter of CoII to be ≈‐14 cm‐1, which is consistent with the magnetothermal and spectroscopic data. Chapter 4 describes the synthesis and characterisation of six magnetic trigonal bipyramids, synthesised through dynamic covalent reactions of the metalloligand [FeIIILNH23] (HLNH2 = 1‐(4‐ aminophenyl)butane‐1,3‐dione) with either a dialdehyde or diacyl dichloride. The three [FeIII2MII3Lim3]n+ (MII = Co, Ni; n = 0‐6) imine‐based cages are formed from the reaction of the metalloligand with 2,6‐pyridinedicarboxaldehyde in the presence of a templating MII salt and a catalytic amount of acid, whereas the three [FeIII2Lam3] amide‐based cages are formed from the reaction of the metalloligand with isophthaloyl chloride in the presence of a base. The [FeIII2NiII3Lim3]n+ trigonal bipyramid displays weak antiferromagnetic interactions between FeIII and NiII ions, with JFe‐Ni = ‐0.12 cm‐1 and DNi = 8.93 cm‐1, while the [FeIII2Lam3] amide‐based cages display interesting configurational features dominated by the enthalpic gain from a series of intermolecular interactions.

The metal-organic framework (MOF) compounds have witnessed rapid growth in the past decade and currently emerged as a highly unique area in the field of chemistry, materials science, and multiple branches of engineering. It presents applications in diverse fields such as gas sorption, catalysis, ionic conductivity, sensing etc. These compounds are built by the inorganic metal ions which are bridged by organic linkers to form extended structures. These compounds are mainly synthesized by either one-pot synthesis or in a sequential manner. In the former case, the inorganic metal ions and the respective organic linker are reacted together in a particular solvent or solvent mixture, whereas in the later case, a metalloligand is prepared by using the organic linker and the primary metal ion, which react with the secondary metal ion forming the desired structure. In this thesis, the synthesis of metal-organic framework compounds by one-pot synthesis as well as the sequential synthesis is presented. The structures of all the synthesized compounds have been determined by single crystal X-ray diffraction technique. The prepared compounds were employed in the study of sensing of nitroaromatic compounds, toxic metal ions and highly oxidizing anions. In addition, detailed studies of heterogeneous catalysis employing the prepared MOFs were investigated along with catalysis by metal nanoparticle incorporated within MOFs. In select cases, the labile nature of the lattice water molecules was established by performing in-situ single crystal to single crystal (SCSC) structural transformation studies. In addition, the proton conductivity and the magnetic behavior have also been studied. Chapter 1 of the thesis presents a brief overview on metal-organic framework compounds and summarizes its various important properties. In chapter 2, the synthesis, structure, and characterization of heterometallic metal-organic framework compounds using 2-mercaptonicotinic (H2mna) and Cu(I) / Ag(I) based two metalloligands, [Cu6(Hmna)6] and [Ag6(Hmna)2(mna)4](NH4)4 are presented. In chapter 3, we present the synthesis, structure and nitroaromatic sensing behavior of [Ag6(mna)6](NH4)6 metalloligand based heterometallic metal-organic framework compounds. In chapter 4, the synthesis, structure and Lewis acid catalytic behavior of 6-mercaptonicotinic acid based heterometallic metal-organic framework compounds are presented. In chapter 5, the stabilization of the palladium nanoparticles in the newly synthesized 1,10-phenanthroline based metal-organic framework compounds and their catalytic behavior is presented. In chapter 6, we present the synthesis, structure and the sensing behavior of hazardous chemicals such as toxic metal ions and highly oxidizing anions. In addition, the adsorption and desorption of synthetic dye molecules by the metal-organic framework compounds are also presented.