Reevaluation of Poly(ethylene-alt-propylene)-block-Polydimethylsiloxane Phase Behavior Uncovers Topological Close-Packing and Epitaxial Quasicrystal Growth.

Reanalysis of an asymmetric poly(ethylene-alt-propylene)-block-polydimethylsiloxane (PEP-PDMS) diblock copolymer first investigated in 1999 has revealed a rich phase behavior including a dodecagonal quasicrystal (DDQC), a Frank-Kasper σ phase, and a body-centered cubic (BCC) packing at high temperature adjacent to the disordered state. On subjecting the sample to large amplitude oscillatory shear well below the σ-BCC order-order transition temperature (TOOT), small-angle X-ray scattering evidenced the emergence of a twinned BCC phase that, on heating, underwent a phase transition to an unusually anisotropic DDQC state. Surprisingly, we observe no evidence of this apparent epitaxy on heating or cooling through the equilibrium σ-BCC transition. We rationalize these results in terms of a shear-induced order-order transition and an apparent BCC-DDQC epitaxy favored by micelle translation-mediated ordering dynamics far below TOOT.

N3-Ligated nickel(ii) diketonate complexes: synthesis, characterization and evaluation of O2 reactivity.

Interest in O2-dependent aliphatic carbon-carbon (C-C) bond cleavage reactions of first row divalent metal diketonate complexes stems from the desire to further understand the reaction pathways of enzymes such as DKE1 and to extract information to develop applications in organic synthesis. A recent report of O2-dependent aliphatic C-C bond cleavage at ambient temperature in Ni(ii) diketonate complexes supported by a tridentate nitrogen donor ligand [(MBBP)Ni(PhC(O)CHC(O)Ph)]Cl (7-Cl; MBBP = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) in the presence of NEt3 spurred our interest in further examining the chemistry of such complexes. A series of new TERPY-ligated Ni(ii) diketonate complexes of the general formula [(TERPY)Ni(R2-1,3-diketonate)]ClO4 (1: R = CH3; 2: R = C(CH3)3; 3: R = Ph) was prepared under air and characterized using single crystal X-ray crystallography, elemental analysis, 1H NMR, ESI-MS, FTIR, and UV-vis. Analysis of the reaction mixtures in which these complexes were generated using 1H NMR and ESI-MS revealed the presence of both the desired diketonate complex and the bis-TERPY derivative [(TERPY)2Ni](ClO4)2 (4). Through selective crystallization 1-3 were isolated in analytically pure form. Analysis of reaction mixtures leading to the formation of the MBBP analogs [(MBBP)Ni(R2-1,3-diketonate)]X (X = ClO4: 5: R = CH3; 6: R = C(CH3)3; 7-ClO4: R = Ph; X = Cl: 7-Cl: R = Ph) using 1H NMR and ESI-MS revealed the presence of [(MBBP)2Ni](ClO4)2 (8). Analysis of aerobic acetonitrile solutions of analytically pure 1-3, 5 and 6 containing NEt3 and in some cases H2O using 1H NMR and UV-vis revealed evidence for the formation of additional bis-ligand complexes (4 and 8) but suggested no oxidative diketonate cleavage reactivity. Analysis of the organic products generated from 3, 7-ClO4 and 7-Cl revealed unaltered dibenzoylmethane. Our results therefore indicate that N3-ligated Ni(ii) complexes of unsubstituted diketonate ligands do not exhibit O2-dependent aliphatic C-C bond clevage at room temperature, including in the presence of NEt3 and/or H2O.

A15, σ, and a Quasicrystal: Access to Complex Particle Packings via Bidisperse Diblock Copolymer Blends.

A renewed focus on the phase behavior of nominally single-component, compositionally asymmetric diblock copolymers has revealed a host of previously unanticipated Frank-Kasper (FK) and quasicrystalline phases. However, these periodic and aperiodic particle packings have thus far only been reported in low molecular weight, highly conformationally asymmetric diblock copolymers, leaving researchers with a relatively small library of polymers in which these phases can be studied. In this work, we report on a simple approach to access these morphologies: blending two diblock copolymers with the same corona block length and varied core block lengths. Compositionally symmetric and asymmetric polystyrene-b-1,4-polybutadiene (SB) diblock copolymers with constant corona block lengths were blended together and shown via small-angle X-ray scattering and transmission electron microscopy to order into the FK A15 and σ phases, as well as a dodecagonal quasicrystal, providing a route to various particle packings in high molecular weight diblock copolymer melts.