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1.
Nat Chem ; 9(7): 644-652, 2017 07.
Artículo en Inglés | MEDLINE | ID: mdl-28644481

RESUMEN

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid-solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.

2.
Science ; 329(5995): 1053-7, 2010 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-20798314

RESUMEN

Porous materials find widespread application in storage, separation, and catalytic technologies. We report a crystalline porous solid with adaptable porosity, in which a simple dipeptide linker is arranged in a regular array by coordination to metal centers. Experiments reinforced by molecular dynamics simulations showed that low-energy torsions and displacements of the peptides enabled the available pore volume to evolve smoothly from zero as the guest loading increased. The observed cooperative feedback in sorption isotherms resembled the response of proteins undergoing conformational selection, suggesting an energy landscape similar to that required for protein folding. The flexible peptide linker was shown to play the pivotal role in changing the pore conformation.


Asunto(s)
Dióxido de Carbono/química , Dipéptidos/química , Zinc/química , Adsorción , Fenómenos Químicos , Cristalización , Difusión , Enlace de Hidrógeno , Ligandos , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Simulación de Dinámica Molecular , Estructura Molecular , Porosidad , Presión , Conformación Proteica , Pliegue de Proteína , Solventes , Termodinámica , Difracción de Rayos X
3.
Phys Rev Lett ; 104(9): 097002, 2010 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-20367005

RESUMEN

We investigate the normal state of the "11" iron-based superconductor FeSe0.42Te0.58 by angle-resolved photoemission. Our data reveal a highly renormalized quasiparticle dispersion characteristic of a strongly correlated metal. We find sheet dependent effective carrier masses between approximately 3 and 16m{e} corresponding to a mass enhancement over band structure values of m{*}/m{band} approximately 6-20. This is nearly an order of magnitude higher than the renormalization reported previously for iron-arsenide superconductors of the "1111" and "122" families but fully consistent with the bulk specific heat.

4.
Phys Rev Lett ; 101(13): 136404, 2008 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-18851470

RESUMEN

Superconductivity emerges for the A15 polymorph of the fulleride Cs3C60 upon compression to a pressure of approximately 4 kbar. Using density functional theory we study the bonding in the A15 phase as a function of unit cell volume comparing it to that in the fcc polymorph. We find that, despite its smaller packing density, the bcc-derived A15 phase has both a substantially wider bandwidth for the partially occupied t1u band and a higher density of states at the Fermi level. This result can be traced to the striking differences in the nature of the interanion Tc--the two sphere packings (body centered versus face centered) observed experimentally produce two electronically distinct classes of fulleride superconductors.

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