ABSTRACT
Polymer mechanochemistry has been established as an enabling tool in accessing chemical reactivity and reaction pathways that are distinctive from their thermal counterparts. However, eliciting diversified reaction pathways by activating different constituent chemical bonds from the same mechanophore structure remains challenging. Here, we report the design of a bicyclo[2.2.0]hexene (BCH) mechanophore to leverage its structural simplicity and relatively low molecular symmetry to demonstrate this idea of multimodal activation. Upon changing the attachment points of pendant polymer chains, three different C-C bonds in bicyclo[2.2.0]hexene are specifically activated via externally applied force by sonication. Experimental characterization confirms that in different scenarios of polymer attachment, the regioisomers of BCH undergo different activation reactions, entailing retro-[2+2] cycloreversion, 1,3-allylic migration, and retro-4π ring-opening reactions, respectively. Control experiments with small-molecule analogues reveal that the observed diversified reactivity of BCH regioisomers is possible only with mechanical force. Theoretical studies further elucidate that the differences in the positions of substitution between regioisomers have a minimal impact on the potential energy surface of the parent BCH scaffold. The mechanochemical selectivity between different C-C bonds in each constitutional isomer is a result of selective and effective coupling of force to the aligned C-C bond in each case.
ABSTRACT
We report the formation of metal-organic cage-crosslinked polymer hydrogels. To enable crosslinking of the cages and subsequent network formation, we used homodifunctionalized poly(ethylene glycol) (PEG) chains terminally substituted with bipyridines as ligands for the Pd6 L4 corners. The encapsulation of guest molecules into supramolecular self-assembled metal-organic cage-crosslinked hydrogels, as well as ultrasound-induced disassembly of the cages with release of their cargo, is presented in addition to their characterization by nuclear magnetic resonance (NMR) techniques, rheology, and comprehensive small-angle X-ray scattering (SAXS) experiments. The constrained geometries simulating external force (CoGEF) method and barriers using a force-modified potential energy surface (FMPES) suggest that the cage-opening mechanism starts with the dissociation of one pyridine ligand at around 0.5â nN. We show the efficient sonochemical activation of the hydrogels HG3 -6 , increasing the non-covalent guest-loading of completely unmodified drugs available for release by a factor of ten in comparison to non-crosslinked, star-shaped assemblies in solution.
