Magnesium Borohydride Confined in a Metal–Organic Framework: A Preorganized System for Facile Arene Hydroboration

In close quarters : When confined in a metal–organic framework, magnesium borohydride reacts with arenes by a hydroboration pathway (see scheme), in contrast to its reactivity under analogous homogeneous solution‐phase conditions. Framework‐imposed organization of the reactive groups is required, which is achieved by a combination of the metal coordination and two hydrogen bonds.

     

Direct observation of the formation of polar nanoregions in Pb(Mg1/3Nb2/3)O3 using neutron pair distribution function analysis

Using neutron pair distribution function analysis over the temperature range from 1000 to 15 K, we demonstrate the existence of local polarization and the formation of medium-range, polar nanoregions (PNRs) with local rhombohedral order in a prototypical relaxor ferroelectric Pb(Mg(1/3)Nb(2/3))O3. We estimate the volume fraction of the PNRs as a function of temperature and show that this fraction steadily increases from 0% to a maximum of approximately 30% as the temperature decreases from 650 to 15 K. Below T approximately 200 K the volume fraction of the PNRs becomes significant, and PNRs freeze into the spin-glass-like state.     

Mechanism for hierarchical self-assembly of nanoparticles on scaffolds derived from block copolymers

Lithographically patterned substrates can direct the self-assembly of block copolymer films into aligned structures that, in turn, template the self-organization of colloidal nanoparticles. Deposition on pristine diblock copolymer films does not lead to reproducible selective decoration, but films modified to have nanoscale corrugation act as scaffolds for highly selective nanoparticle adsorption. The mechanism for this selectivity relies on the lateral forces inherent to spin casting to remove all of the nanoparticle suspension not confined within the nanoscopic trenches. This technique does not rely on interactions between the surfactant capping molecules and the polymer and is therefore general to a wide class of nanoparticle materials. Prospects to obtain long-range ordering and associated potential applications are discussed.     

Chiral II-VI semiconductor nanostructure superlattices based on an amino acid ligand

Reaction of L-cysteine with M(NO3)2 x xH2O (M = Cd, Zn) generates M(L-cysteinate), which feature one-dimensional substructures that can be viewed as fragments of bulk structures of CdS (rock salt high pressure phase) and ZnS (wurtzite) because of the bridging modes accessible to the sulfur atom of L-cysteine. The MS substructures are arranged in a regular and periodic fashion within the crystal via the carboxylate function of L-cysteine. Considering the structural similarities with bulk materials, the optical properties of M(L-cysteinate) were studied and indicate blue shifts of the band gap of 2.59 eV (M = Cd, compared to CdS rock salt) and 1.37 eV (M = Zn, compared to ZnS wurtzite) with respect to the bulk MS structures, due to the low dimensionality of the metal-sulfur arrangement. The chelating nature of the cysteine ligand imposes an unusual mer arrangement of three binding S moieties at Cd with a correspondingly high Cd coordination number in a chalcogenide-based material. Density of states calculations show strong electronic structure similarities with the bulk phases and rationalize the band gap changes.     

Isolating the effect of torsional defects on mobility and band gap in conjugated polymers

Conjugated polymers represent a promising class of organic semiconductors with potential applications in a variety of molecular devices. Poly(3-alkylthiophene)s, in particular, are garnering interest due to their large charge carrier mobility and band gap in the visible region of the spectrum. Defects play a pivotal role in determining the performance of polymer electronics, and yet the function of specific types of defects is still largely unknown. Density functional theory calculations of alkyl-substituted oligothiophenes are used to isolate the effect of static inter-ring torsion defects on key parameters such as electronic coupling between rings and band gap. Results have potential implications both for the fundamental understanding of intramolecular charge transport and for improving processing in organic devices.     

Syntheses, structural characterization and properties of transition metal complexes of 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)-4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt)

The hydrothermal chemistry of a variety of M(II)SO(4) salts with the tetrazole (Ht) ligands 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt) was investigated. In the case of Co(II), three phases were isolated, two of which incorporated sulfate: [Co(5)F(2)(dbdt)(4)(H(2)O)(6)]·2H(2)O (1·2H(2)O), [Co(4)(OH)(2)(SO(4))(bdt)(2)(H(2)O)(4)] (2) and [Co(3)(OH)(SO(4))(btt)(H(2)O)(4)]·3H(2)O (3·3H(2)O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co(5)F(2)(tetrazolate)(8)(H(2)O)(6)}, the tetranuclear {Co(4)(OH)(2)(SO(4))(2)(tetrazolate)(6)}(4-), and the trinuclear {Co(3)(μ(3)-OH)(SO(4))(2) (tetrazolate)(3)}(2-) for 1, 2, and 3, respectively. The Ni(II) analogue [Ni(2)(H(0.67)bdt)(3)]·10.5H(2)O (4·10.5H(2)O) is isomorphous with a fourth cobalt phase, the previously reported [Co(2)(H(0.67)bat)(3)]·20H(2)O and exhibits a {M(tetrazolate)(3/2)}(∞) chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)] (5) consists of {ZnN(4)}tetrahedra linked through bdt ligands bonding through N1,N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(II) material (Me(2)NH(2))(3)[Cd(12)Cl(3)(btt)(8)(DMF)(12)]·xDMF·yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd(4)Cl(tetrazolate)(8)(DMF)(4)}(1-) secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(II) series are reflective of the structural building units.