Developments in Dynamic Covalent Chemistries from the Reaction of Thiols with Hexahydrotriazines.
Dynamic covalent chemistries have garnered significant attention for their potential to revolutionize technologies in the material fields (engineering, biomedical, and sensors) and synthetic design strategies as they provide access to stimuli responsiveness and adaptive behaviors. However, only a limited number of molecular motifs have been known to display this dynamic behavior under mild conditions. Here, we identified a dynamic covalent motif-thioaminals-that is produced from the reaction of hexahydrotriazines (HTs) with thiols. Furthermore, we report on the synthesis of a new family of step-growth polymers based on this motif. The condensation efficiently proceeds to quantitative yields within a short time frame and offers versatility in functional group tolerance; thus, it can be exploited to synthesize both small molecule thioaminals as well as high molecular weight polymers from the step-growth polymerization of HTs with dithiols. Careful evaluation of substituted HTs and organic thiols supported by DFT calculations led to a chemically diverse library of polymers based on this motif. Finally, dynamic substitution reactions were employed toward the facile preparation of functional oligomers and macromolecules. This dynamic covalent motif is particularly attractive for a range of applications that include material design and drug delivery due to the economic feasibility of synthesis.
IBM Almaden Research Center , San Jose, California 95120, United States.
Rudy J
RJ
Wojtecki
IBM Almaden Research Center , San Jose, California 95120, United States.
Gavin O
GO
Jones
IBM Almaden Research Center , San Jose, California 95120, United States.
Alexander Y
AY
Yuen
Institute of Bioengineering and Nanotechnology , 31 Biopolis Way, The Nanos, #04-01, Singapore 138669.
Willy
W
Chin
IBM Power Systems Hardware Development , Austin, Texas 78758, United States.
Dylan J
DJ
Boday
IBM Almaden Research Center , San Jose, California 95120, United States.
Alshakim
A
Nelson
IBM Almaden Research Center , San Jose, California 95120, United States.
Jeannette M
JM
García
Institute of Bioengineering and Nanotechnology , 31 Biopolis Way, The Nanos, #04-01, Singapore 138669.
Yi Yan
YY
Yang
IBM Almaden Research Center , San Jose, California 95120, United States.
James L
JL
Hedrick