Enabling Selective Mechanochemical Scission of Network Crosslinks by Exchanging Single Carbon Atoms for SiliconClick to copy article linkArticle link copied!
- Sophia J. MelvinSophia J. MelvinDepartment of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United StatesMore by Sophia J. Melvin
- Yunxin YaoYunxin YaoDepartment of Chemistry, Duke University, Durham, North Carolina 27710, United StatesMore by Yunxin Yao
- Xiao HuangXiao HuangDepartment of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesMore by Xiao Huang
- Rowina C. BellRowina C. BellDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Rowina C. Bell
- Ryann E. KemmerlingRyann E. KemmerlingDepartment of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United StatesMore by Ryann E. Kemmerling
- Ilia KevlishviliIlia KevlishviliDepartment of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesMore by Ilia Kevlishvili
- Angus C. BergAngus C. BergDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Angus C. Berg
- Ana Paula Kitos VasconcelosAna Paula Kitos VasconcelosDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Ana Paula Kitos Vasconcelos
- Alshakim NelsonAlshakim NelsonDepartment of Chemistry, University of Washington, Seattle, Washington 98195, United StatesMore by Alshakim Nelson
- Heather J. KulikHeather J. KulikDepartment of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesDepartment of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesMore by Heather J. Kulik
- Stephen L. CraigStephen L. CraigDepartment of Chemistry, Duke University, Durham, North Carolina 27710, United StatesMore by Stephen L. Craig
- Rebekka S. Klausen*Rebekka S. Klausen*Email: [email protected]Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United StatesMore by Rebekka S. Klausen
Abstract
The tearing of a polymer network arises from mechanochemically coupled bond-breaking events in the backbone of a polymer chain. An emerging research area is the identification of molecular strategies for network toughening, such as the strategic placement of mechanochemically reactive groups (e.g., scissile mechanophores) in the crosslinks of a network instead of in the load-bearing primary strands. These mechanically labile crosslinkers have typically relied on release of ring strain or weak covalent bonds for selective covalent bond scission. Here, we report a novel chemical design for accelerated mechanochemical bond scission based on replacing a single carbon atom in a crosslinker with a silicon atom. This single-atom replacement affords up to a two-fold increase in the tearing energy. We suggest a mechanism, validated by computational modeling, for accelerated mechanochemical Si–C bond scission based on minimizing the energy required to distort the starting material toward the transition-state geometry. We demonstrated the seamless incorporation of these scissile carbosilanes to toughen 3D-printed networks, which demonstrates their suitability for additive manufacturing processes.
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