The rapid and uncontrolled nature of network formation from di(meth)acrylate monomers produces high shrinkage stress and results in polymers with oftentimes brittle mechanical properties. Methods for regulating polymerization and network formation are sought. One option is the use of addition-fragmentation chain transfer (AFCT) agents, which are well known to control molecular weight and molecular weight distribution of monofunctional (meth) acrylates. A series of novel and previously described AFCT reagents were synthesized and screened with laser flash photolysis to determine reactivity. Well-performing AFCT reagents were then tested in polymerizations with monofunctional and difunctional methacrylates. With monofunctional monomers, the molecular weight and polydispersity of the resultant linear polymers tend to decrease with the addition of AFCT agent. In copolymerization with dimethacrylate monomers, the AFCT agents were found to substantially lower and sharpen the glass transition. Sharpness of the glass transition is here indicative of a more regular and homogenous network. After coupling of the instruments, photorheology was performed simultaneously with real-time IR to show an increase in monomer conversion at the time of gelation, which appears to have a positive effect on reducing shrinkage stress. (C) 2015 Wiley Periodicals, Inc.