394 research outputs found
Soap Froths and Crystal Structures
We propose a physical mechanism to explain the crystal symmetries found in
macromolecular and supramolecular micellar materials. We argue that the packing
entropy of the hard micellar cores is frustrated by the entropic interaction of
their brush-like coronas. The latter interaction is treated as a surface effect
between neighboring Voronoi cells. The observed crystal structures correspond
to the Kelvin and Weaire-Phelan minimal foams. We show that these structures
are stable for reasonable areal entropy densities.Comment: 4 pages, RevTeX, 2 included eps figure
Effect of interchain coupling on conducting polymer luminescence: excimers in derivatives of poly(phenylene vinylene)
Optical excitation of a chain in a polymer film may result in formation of an
excimer, a superposition of on-chain excitons and charge-transfer excitons on
the originally excited chain and a neighboring chain. The excimer emission is
red-shifted compared to that of an on-chain exciton by an amount depending on
the interchain coupling . Setting up the excimer wavefunction and
calculating the red shift, we determine average values, referred to a
monomer, of 0.52 eV and 0.16 eV for poly(2,5-hexyloxy -phenylene
cyanovinylene), CN-PPV, and poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1, 4
p-phenylene vinylene], MEH-PPV, respectively, and use them to determine the
effect of interchain distance on the emission.Comment: 10 pages, RevTeX, 1 PS figure, replaced version of cond-mat/9707095,
accepted for publication in Phys. Rev. B, Rapid Communicatio
Hydration of a side-chain-free n-type semiconducting ladder polymer driven by electrochemical doping
We study the organic electrochemical transistors (OECTs) performance of the
ladder polymer, poly(benzimidazobenzophenanthroline) (BBL) in an attempt to
better understand how an apparently hydrophobic side-chain-free polymer is able
to operate as an OECT with favorable redox kinetics in an aqueous environment.
We examine two BBLs of different molecular masses from different sources. Both
BBLs show significant film swelling during the initial reduction step. By
combining electrochemical quartz crystal microbalance (eQCM) gravimetry,
in-operando atomic force microscopy (AFM), and both ex-situ and in-operando
grazing incidence wide-angle x-ray scattering (GIWAXS), we provide a detailed
structural picture of the electrochemical charge injection process in BBL in
the absence of any hydrophilic side-chains. Compared with ex-situ measurements,
in-operando GIWAXS shows both more swelling upon electrochemical doping than
has previously been recognized, and less contraction upon dedoping. The data
show that BBL films undergo an irreversible hydration driven by the initial
electrochemical doping cycle with significant water retention and lamellar
expansion that persists across subsequent oxidation/reduction cycles. This
swelling creates a hydrophilic environment that facilitates the subsequent fast
hydrated ion transport in the absence of the hydrophilic side-chains used in
many other polymer systems. Due to its rigid ladder backbone and absence of
hydrophilic side-chains, the primary BBL water uptake does not significantly
degrade the crystalline order, and the original dehydrated, unswelled state can
be recovered after drying. The combination of doping induced hydrophilicity and
robust crystalline order leads to efficient ionic transport and good stability.Comment: 24 pages, 5 figure
Origin of spectral broadening in pi-conjugated amorphous semiconductors
We present a study of the picosecond fluorescence dynamics of pi-conjugated semiconducting organic dendrimers in the solid state. By varying the degree of branching within the dendrons, referred to as the dendrimer generation, a control of intermolecular spacing of the emissive core and therefore of the lattice parameter for Forster-type energy transfer is achieved. This allows a distinction between spectral diffusion and excimer formation as the two main sources of spectral broadening in organic semiconductors. Whereas Forster-type dispersive spectral relaxation is independent of temperature but strongly dependent on the interchromophore distance, excimer formation is also strongly thermally activated due to temperature-dependent conformational changes and the influence of thermally activated dynamic disorder. The rapid spectral diffusion allows a determination of the excimer rise in the emission, which is shown to have a profound impact on the steady state luminescence properties of dendrimer films. We show that the dendrimer generation not only allows a microscopic control of intermolecular interactions but also a direct control of the rate of spectral diffusion. Implications for the design of novel materials for optoelectronic devices are discussed
Blue-Emitting Butterfly-Shaped 1,3,5,9-Tetraarylpyrenes: Synthesis, Crystal Structures, and Photophysical Properties
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters (copyright © American Chemical Society) after peer review and technical editing by the publisher. To access the final edited and published work see: http://dx.doi.org/10.1021/ol400265
Block Conjugated Copolymers: Toward Quantum-Well Nanostructures for Exploring Spatial Confinement Effects on Electronic, Optoelectronic, and Optical Phenomena
2,3,6,7-Tetraamino-9,9-bis(2-ethylhexyl)fluorene: New Multifunctional Monomer for Soluble Ladder-Conjugated Molecules and Polymers
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