One of the great challenges for chemistry is the development of new materials that reduce our society's dependence on critical and expensive metals such as rare earth elements. In this context, a general long-term research objective of many research groups throughout the world is the synthesis of novel magnetic materials that would employ molecular radicals as key building blocks. The use of organic compounds for such purpose is highly desirable as it would allow significant benefits over purely metallic systems such as solubility, multifunctionality, and chemical rather than metallurgical processability. The challenge herein lies in developing new organic radicals that are indefinitely stable under standard ambient conditions but still structurally tunable to attain the desired properties. The present project sought new solutions for these problems with an objective to synthesise new families of stable organic radicals and to explore their solid state properties including, but not limited to, crystallization, coordination chemistry, and magnetism.