Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.
In this feature article, the development of linear quadruple hydrogen bonded systems is discussed, emphasizing applications in supramolecular chemistry and self-assembly.
This review aims to provide a field guide for the implementation of mechanochemistry in synthetic polymers by summarizing the molecules, materials, and methods that have been developed in this field.
The effect of stacking of end groups on the rheological behavior of supramolecular polymer melts is reported. Oscillatory shear experiments in the transition zone from the pseudo rubber plateau to the flow region of telechelic polycaprolactones (PCLs) with ureidopyrimidinone (UPy) end groups directly attached to PCL can be fitted with a single Maxwell element. This demonstrates that dimerization of the UPy groups is unidirectional and that reversible chain scission is faster than reptation. If the UPy groups are connected to the polymer via a urethane linker, a low-frequency plateau in G′ is observed. This is ascribed to the formation of a network of stacked UPy dimers, aided by urethane hydrogen bonding. Below their melting point, these stacks form long fibers in the urethane linked supramolecular poly(methyl caprolactone), which were observed with atomic force microscopy (AFM). Steric hindrance interferes with stacking, since the plateau in G′ is lower in a urethane linked polymer with bulky adamantyl-UPy end groups.
Diels–Alder adducts of π-extended anthracenes have been synthesised, employed as mechanophores in polymeric materials and show unprecedented detection sensitivity for mechanical stress.
Telechelic oligo- and poly(dimethylsiloxanes) 1 and 2, with two ureidopyrimidone (UPy)
functional groups, have been prepared via a hydrosilylation reaction. The compounds have been
characterized in solution by 1H NMR and viscometry and in the solid state by 1H NMR and 13C NMR,
FTIR, and rheology measurements. The measurements show that the UPy groups of 1 and 2 are associated
via quadruple hydrogen bonds in a donor−donor−acceptor−acceptor (DDAA) array. In many aspects,
the materials behave like entangled, high molecular weight polymers. Compound 2 has a T
g at −119 °C
and shows melting of microcrystalline domains of associated UPy units at −25 °C. Compound 1 has a
crystalline form (T
m = 112 °C) and an amorphous modification with a T
g of 25 °C. Solid-state NMR was
used to investigate the mobility of these phases. WISE spectra show a higher mobility of the UPy groups
in the amorphous phase than in the crystals of 1. Amorphous 1 and 2 behave like entangled polymers.
Their mechanical behavior is characterized by a rubbery plateau and a relatively high activation enthalpy
for stress relaxation (ΔH = 127 kJ/mol for 1; ΔH = 54 kJ/mol for 2), which was derived from the
temperature dependence of the zero-shear viscosity. Estimates for the degree of polymerization (DP) of
1 and 2, based on the mechanical properties, give DP > 100 for 1 and approximately 20 for 2. Like in
condensation polymerization, the DP's of reversible supramolecular polymers are presumably limited by
the presence of small amounts of monofunctional impurities.
A classic paradigm of soft and extensible polymer materials is the difficulty of combining reversible elasticity with high fracture toughness, in particular for moduli above 1 MPa. Our recent discovery of multiple network acrylic elastomers opened a pathway to obtain precisely such a combination. We show here that they can be seen as true molecular composites with a well-cross-linked network acting as a percolating filler embedded in an extensible matrix, so that the stress-strain curves of a family of molecular composite materials made with different volume fractions of the same cross-linked network can be renormalized into a master curve. For low volume fractions (<3%) of cross-linked network, we demonstrate with mechanoluminescence experiments that the elastomer undergoes a strong localized softening due to scission of covalent bonds followed by a stable necking process, a phenomenon never observed before in elastomers. The quantification of the emitted luminescence shows that the damage in the material occurs in two steps, with a first step where random bond breakage occurs in the material accompanied by a moderate level of dissipated energy and a second step where a moderate level of more localized bond scission leads to a much larger level of dissipated energy. This combined use of mechanical macroscopic testing and molecular bond scission data provides unprecedented insight on how tough soft materials can damage and fail.
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