The molecular characteristics of the first five generations of poly(propyleneimine) dendrimers with two different types of end groups have been investigated using small-angle neutron scattering (SANS), viscosimetry, and molecular dynamics simulations. The dimension of the poly(propyleneimine) dendrimers, as measured by both SANS and viscosimetry, increases linearly with the generation number and roughly as M 1/3 , where M is the molar mass of the dendrimer. This relationship proves to be independent of the character of the end group and the solvent used and is indicative of a compact (space-filling) structure with a fractal dimensionality of approximately 3. The distinct maximum in the Kratky representation of the scattering data and the observed relation (i.e., R η = (5/3)R g ) between the hydrodynamic radius Rη and the radius of gyration Rg are consistent with such a structure. Molecular dynamics simulations for two different solvent qualities are in good accordance with the acquired experimental results. The probability distributions of the amine end groups, based on these simulations, exhibit a substantial degree of backfolding. The corresponding radial density distributions show a constant density plateau and a monotonic decrease of the density toward the exterior of the molecule. The above results indicate that the poly(propyleneimine) dendrimers can be considered as flexible molecules with a relatively homogeneous radial density distribution. This view clearly deviates from both the dense shell and dense core models.
A systematic study on the effect of molecular structure on the photoinitiated polymerization
of acrylates was undertaken. Initially, the research was focused on the effect of hydrogen bonding, and
it was found that preorganization via hydrogen bonding enhances the maximum rate of polymerization
(R
p). This hydrogen bonding facilitated preorganization also affected the tacticity of the resultant polymer.
Next, the effect of polarity as represented by the calculated dipole moment (μcalc) of a given monomer was
investigated. A direct linear correlation between R
p and the calculated Boltzmann-averaged dipole moment
(μcalc) was observed. The R
p−μcalc correlation holds for pure monomers, mixtures of monomers, and even
mixtures of monomers with inert solvents. This correlation enables the rational design of monomers with
a required reactivity. In addition, these studies suggest that the propagation step of polymerization is
influenced by hydrogen bonding while the dipole moment influences the termination rate constant. These
two mechanistic explanations can be regarded as complementary factors that influence the speed of
acrylate polymerization.
X-ray crystal structures of a series of cationic (P-P)palladium(1,1-(CH(3))(2)C(3)H(3)) complexes (P-P = dppe (1,2-bis(diphenylphosphino)ethane), dppf (1,1'-bis(diphenylphosphino)ferrocene), and DPEphos (2,2'-bis(diphenylphosphino)diphenyl ether)) and the (Xantphos)Pd(C(3)H(5))BF(4) (Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) complex have been determined. In the solid state structure, the phenyl rings of the ligand are oriented in the direction of the nonsymmetrically bound [1,1-(CH(3))(2)C(3)H(3)] moiety. An increase of the bite angle of the chelating ligand results in an increase of the cone angle. In complexes containing ligands having a large cone angle, the distances between the phenyl rings and the allyl moiety become small, resulting in a distortion of the symmetry of the palladium-allyl bond. In solution, two types of dynamic exchange have been observed, the pi-sigma rearrangement and the apparent rotation of the allyl moiety. At the same time, the folded structure of the ligand changes from an endo to an exo orientation or vice versa. The regioselectivity in the palladium-catalyzed allylic alkylation of 3-methyl-but-2-enyl acetate is determined by the cone angle of the bidentate phosphine ligand. Nucleophilic attack by a malonate anion takes place preferentially at the allylic carbon atom having the largest distance to palladium. Ligands with a larger cone angle direct the regioselectivity to the formation of the branched product, from 8% for dppe (1) to 61% found for Xantphos (6). The influence of the cone angle on the regioselectivity has been assigned to a sterically induced electronic effect.
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