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This talk will describe our efforts to control the structure of synthetic polymers from single-chains to networks.Motivated by nature,polymer chemists have long sought methods and strategies for the synthesis of polymers with precise structure.Existing methods for precision polymer synthesis typically require a trade-off between structural control and atom economy/scalability.Seeking more efficient strategies,we have developed an iterative exponential growth plus sidechain functionalization (IEG+) approach that enables reasonably efficient gram-scale syntheses of macromolecules with absolute control over mass,sequence,and stereochemistry.This talk will focus on the synthesis and applications of IEG+ polymers,the latter of which include self-assembly and biological properties.