In the past fifty years there have been increased concerns about the impact of pollutants not only on humans, but also on the environment. Significant progress has been made in several key research areas, such as catalysis, the design of safer chemicals and en~ironmentally begnin solvents. However, the constant demand for new materials exhibiting improved physico-chemical properties and commercial advantages within a green chemistry approach renders the development of new t'. . polymer chemistries a very challenging prospect. As a consequence, nitrogen based photochemical reagents raised a lot of interest and attention, since these photoactive substrates may respond to the criteria and principles imposed by 'Green. Chemistry'. Indeed, three membered diazirine rings can generate a very reactive carbene species by the extrusion of a nitrogen molecule upon activation either via ultrasonic, thermal, or photochemical means, and can combine with a broad range of functional groups to create new covalent bonds. Hence, as part of a programme undertaken at the University of Reading, new AB, AB2 and A2+B3 monomers have been targeted and identified. The homo/co polymerisations of 3,5 diallyloxy phenyl-3-methyldiazirine or 1,4-di(methyl diazirine) benzene associated with 1,3,5-tri(hydroxyl) benzene have been realized. In order to benefit from the advantages displayed by diazirines with regard to their chemical stability, preparation and potential applications, the monomers reported here all feature photoactive diazirine rings in conjunction with secondary functionalities such as alkenes or free hydroxyls. It was envisaged that these new diazirine monomer systems would lead to the development of new materials of diverse topologies that may be polymerised photoactively or thermally in situ upon the substrate surface and the preliminary studies in this area are reported in this thesis.