The mechanical strength of scissile chemical bonds plays a role in material failure and in the mechanical activation of latent reactivity, but quantitative measures of mechanical strength are rare. Here, we report the relative mechanical strength of polymers bearing three putatively "weak" scissile bonds: the carbon-nitrogen bond of an azobisdialkylnitrile (<30 kcal mol(-1)), the carbon-sulfur bond of a thioether (71-74 kcal mol(-1)), and the carbon-oxygen bond of a benzylphenyl ether (52-54 kcal mol(-1)). The mechanical strengths are assessed in the context of chain scission triggered by pulsed sonication of polymer solutions, by using two complementary techniques: (i) the competition within a single polymer chain between the bond scission of interest and the nonscissile mechanochemical ring opening of gem-dichlorocyclopropane mechanophores and (ii) the molecular weights at long (4 h) sonication times of multimechanophore polymers. The two methods produce a consistent story: in contrast to their thermodynamic strengths, the relative mechanical strengths of the three weak bonds are azobisdialkylnitrile (weakest) < thioether < benzylphenyl ether. The greater mechanical strength of the benzylphenyl ether relative to the thermodynamically stronger carbon-sulfur bond is ascribed to poor mechanochemical coupling, at least in part as a result of the rehybridization that accompanies carbon-oxygen bond scission.
Metal-organic frameworks (MOFs) have shown great promise in catalysis, mainly due to their high content of active centers, large internal surface areas, tunable pore size, and versatile chemical functionalities. However, it is a challenge to rationally design and construct MOFs that can serve as highly stable and reusable heterogeneous catalysts. Here two new robust 3D porous metal-cyclam-based zirconium MOFs, denoted VPI-100 (Cu) and VPI-100 (Ni), have been prepared by a modulated synthetic strategy. The frameworks are assembled by eight-connected Zr clusters and metallocyclams as organic linkers. Importantly, the cyclam core has accessible axial coordination sites for guest interactions and maintains the electronic properties exhibited by the parent cyclam ring. The VPI-100 MOFs exhibit excellent chemical stability in various organic and aqueous solvents over a wide pH range and show high CO uptake capacity (up to ∼9.83 wt% adsorption at 273 K under 1 atm). Moreover, VPI-100 MOFs demonstrate some of the highest reported catalytic activity values (turnover frequency and conversion efficiency) among Zr-based MOFs for the chemical fixation of CO with epoxides, including sterically hindered epoxides. The MOFs, which bear dual catalytic sites (Zr and Cu/Ni), enable chemistry not possible with the cyclam ligand under the same conditions and can be used as recoverable stable heterogeneous catalysts without losing performance.
The first supramolecular star polymer based on pseudorotaxane host-guest complexation was prepared from statistical complexation of a homotritopic tris(crown ether) host and monotopic paraquat-terminated polystyrene guest in solution. The formation of this supramolecular star polymer was confirmed by proton NMR characterization and viscosity studies.
The single-crystal X-ray structure of Ru(3)(CO)(12) is reported at 8 pressures ranging from 1 atm (0.0 GPa) to 8.14(5) GPa. Although intramolecular bonding parameters remain relatively constant, intramolecular and intermolecular nonbonding contact distances decrease by an average of 4% and 15%, respectively. At 8.14 GPa, O...O, C...O, and C...C intermolecular distances as short as 2.54(4), 2.64(6), and 3.07(4) A, respectively, are observed, and the unit cell compresses to 75% of the ambient pressure volume. Raman and infrared spectroscopic measurements show that carbonyl stretching frequencies shift to higher wavenumber values by as much as 80 cm(-)(1), even though Ru-C and C-O distances stay roughly constant throughout the entire pressure range studied. Compression of the sample to above 18 GPa with laser radiation results in an irreversible transformation due to either decomposition or a total collapse of D(3)(h) molecular geometry accompanied by color darkening.
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