Polymer materials are of high importance for technological advancement in commercial, military, and biomedical applications. While most synthesis in a commercial or bulk synthesis scale focuses on linear polymers, no technology exists for synthesis of macrocycles in various controlled entanglements. In this invention, the concepts and paradigms of Knot Theory will guide the design of specific molecular and supramolecular templates providing rational precursors for new molecular topologies of macrocycles and macropolycycles. Different companies as well as military or biomedical firms have high interest for this type of materials. Controlled entanglement will enable new thermo-mechanical polymer properties and processing conditions previously unrealized. The main challenge is in controlled knot formation via in-situ living free-radical polymerization in a ring insertion polymerization (RIP) - reversible addition fragmentation chain transfer (RAFT) process. In general, supramolecularly templated iniferters for RAFT polymerization is an area that has remained largely unexplored in macromolecular synthesis. In this manner, intricately ordered supramolecular assemblies previously developed in small molecules can be creatively used to synthesize new large macromolecular structures of high value for polymer theory, de nova polymer synthesis, and practical industrial applications of "knotty polymers ". The invention if successful can potentially impact the use and applications of polymer materials. Unique macromolecular, physical, and chemical properties are expected based on linear vs. cyclic macromolecule comparison. Thermo-mechanical properties are expected to differ considerably from its linear polymer counterparts. Blends of macrocycles with linear components may induce a combination of mechanical properties yet unrealized. A wide variety of model cyclic and knotted polymers will be made available for fundamental studies for the first time. Possible technological applications can include compatibilizers, lubricants, surfactants, colloidal particles, and tissue engineering.