We report the design and synthesis of a class of hybrid latex particle that combines the elastomeric properties of polyolefins with the physicochemical diversity of acrylics. These hybrid polyolefin-acrylic particles are obtained in two steps, starting from the mechanical dispersion of a polyolefin resin to yield a colloidally stable particle dispersion, which is then used in a second step as a seed for the free radical emulsion polymerization of an acrylic phase. Imaging of the resulting particles by scanning electron and atomic force microscopy reveals a distinct lobed morphology, where acrylic polymer is associated with the surface of the polyolefin dispersion. Using gel permeation chromatography (GPC), we quantify the degree of grafting between the core and the acrylic phase, while analysis by dynamic mechanical analysis (DMA) shows that key properties of the polyolefin remain unaffected by the emulsion polymerization process. Process changes including varying the polyolefin/acrylic ratio, monomer addition method, initiator type, and acrylic composition can be used to control the surface coverage and size of the acrylic lobes, and therefore tune the particle morphology. This approach is modular both in terms of the polyolefin materials and additives that can be used to fabricate the core, as well as the physicochemical properties of the acrylic phase (composition, glass transition temperature, chemical functionality, etc.) and provides opportunities to design hybrid particles for a range of advanced applications.

The aryl/methyl fragmentation selectivities for the photo oxidations of phenyltrimethylstannane and (4-methylphenyl)trimethylstannane by 1,2,4,5-tetracyanobenzene in acetonitrile were found to depend on the codonor used to generate the stannane cation radical intermediates. The aryl/methyl fragmentation selectivities for phenyltrimethylstannane and (4-methylphenyl)trimethylstannane varied by factors of 26 and 5.6, respectively, depending on the structures of the codonors. The fragmentation selectivities could be correlated with the oxidation potentials of the codonors and their steric bulk. The results can be interpreted by the intermediacy of heterodimer cation radicals formed between the stannane cation radicals and the neutral codonors, which thereby affect the fragmentation selectivities.

Aryltrialkylstannane cation radicals were generated and characterized by nanosecond transient absorption spectroscopy. Kinetics show the fragmentations of the stannane cation radicals occur by a bimolecular, nucleophile-assisted mechanism (S(N)2). Consistent with this hypothesis, steric effects on both the nucleophile and the stannane cation radicals were observed. Steady-state, preparative photooxidation experiments show that aryltrimethylstannane cation radicals have an unusual preference for loss of aryl radicals over methyl radicals and that the selectivity for aryl vs methyl radical loss is dependent on the identity of the nucleophile. The preference for loss of aryl radicals is rationalized by a hypothesis based on Bent's rules.

The redox equilibrium method was used to determine accurate oxidation potentials in acetonitrile for 40 heteroatom-substituted compounds. These include methoxy-substituted benzenes and biphenyls, aromatic amines, and substituted acetanilides. The redox equilibrium method allowed oxidation potentials to be determined with high precision (≤ ±6 mV). Whereas most of the relative oxidation potentials follow well-established chemical trends, interestingly, the oxidation potentials of substituted N-methylacetanilides were found to be higher than those of the corresponding acetanilides. Density functional theory calculations provided insight into the origin of these surprising results in terms of the preferred conformations of the amides versus their cation radicals.

As we reported recently, endergonic to mildly exergonic electron transfer between neutral aromatics (benzenes and biphenyls) and their radical cations in acetonitrile follows a Sandros-Boltzmann (SB) dependency on the reaction free energy (ΔG); i.e., the rate constant is proportional to 1/[1 + exp(ΔG/RT)]. We now report deviations from this dependency when one reactant is sterically crowded: 1,4-di-tert-butylbenzene (C1), 1,3,5-tri-tert-butylbenzene (C2), or hexaethylbenzene (C3). Obvious deviation from SB behavior is observed with C1. Stronger deviation is observed with the more crowded C2 and C3, where steric hindrance increases the interplanar separation at contact by ~1 Å, significantly decreasing the π orbital overlap. Consequently, electron transfer (k(et)) within the contact pair becomes slower than diffusional separation (k(-d)), causing deviation from the SB dependency, especially near ΔG = 0. Fitting the data to a standard electron-transfer theory gives small matrix elements (~5-7 meV) and reasonable reorganization energies. A small systematic difference between reactions of C3 with benzenes vs biphenyls is rationalized in terms of small differences in the electron-transfer parameters that are consistent with previous data. The influence of solvent viscosity on the competition between k(et) and k(-d) was investigated by comparing reactions in acetonitrile and propylene carbonate.

Nanosecond transient absorption methods were used to determine accurate oxidation potentials (E(ox)) in acetonitrile for benzene and a number of its alkyl-substituted derivatives. E(ox) values were obtained from a combination of equilibrium electron-transfer measurements and electron-transfer kinetics of radical cations produced from pairs of benzene and biphenyl derivatives, with one member of the pair acting as a reference. Using a redox-ladder approach, thermodynamic oxidation potentials were determined for 21 benzene and biphenyl derivatives. Of particular interest, E(ox) values of 2.48 +/- 0.03 and 2.26 +/- 0.02 V vs SCE were obtained for benzene and toluene, respectively. Because of a significant increase in solvent stabilization of the radical cations with decreasing alkyl substitution, the difference between ionization and oxidation potentials of benzene is approximately 0.5 eV larger than that of hexamethylbenzene. Oxidation potentials of the biphenyl derivatives show an excellent correlation with substituent sigma+ values, which allows E(ox) predictions for other biphenyl derivatives. Significant dimer radical cation formation was observed in several cases and equilibrium constants for dimerization were determined. Methodologies are described for determining accurate electron-transfer equilibrium constants even when dimer radical cations are formed. Additional equilibrium measurements in trifluoroacetic acid, methylene chloride, and ethyl acetate demonstrated that solvation differences can substantially alter and even reverse relative E(ox) values.