Electric field distribution in polymer light-emitting electrochemical cells

We use electroabsorption spectroscopy and modeling studies to probe the electric field in light-emitting electrochemical cells. At room temperature and constant applied bias, the steady-state internal field is zero for a range of biases. However, when the ions are frozen in place by cooling under steady bias, and the bias is subsequently changed, the profile of the electric potential resembles a typical p-n junction.     

Selective oxidation of cyclohexanol and 2-cyclohexen-1-ol on O/Au(111): the effect of molecular structure

We combine reactivity studies with infrared reflection absorption spectroscopy to provide molecular-scale insights into the oxidation of two cyclic alcohols, cyclohexanol and 2-cyclohexen-1-ol, by atomic oxygen adsorbed on Au(111). The two alcohols share common features in their reaction pathways: they are both activated by Br?nsted acid-base reactions with adsorbed oxygen. Cyclic ketones, cyclohexanone and 2-cyclohexen-1-one, are the major products, formed from cyclohexanol and 2-cyclohexen-1-ol, respectively. These ketones also undergo secondary ring C-H bond activation. The product distributions reflect a substantial difference in the secondary reactions for these two ketones, which correlate with their gas-phase acidity. The allylic alcohol (2-cylohexen-1-ol) has a greater degree of ring C-H activation, yielding the diketone (2-cyclohexene-1,4-dione) and phenol. Our results provide clear evidence for the importance of C═C functionalities in determining the reactivity of molecules in heterogeneous oxidative transformations promoted on Au-based materials.     

High-performance electron-transporting polymers derived from a heteroaryl bis(trifluoroborate)

In this communication, we report that dipotassium aryl bis(trifluoroborate)s make stable and easy-to-purify yet reactive monomers under Suzuki polycondensation reactions. A bis(trifluoroborate) of 2-alkylbenzotriazole was prepared successfully and copolymerized with dibromobenzothiadiazole in the presence of a Pd catalyst and LiOH, yielding high molecular weight conjugated polymers. This polymer (P1) composed of all electron-accepting units shows excellent electron-transport properties (μ(e) = 0.02 cm(2) V(-1) s(-1)), which proves the value of the aryl bis(trifluoroborate) monomers and suggests that many other types of semiconducting polymers that could not be accessed previously can be synthesized using this approach.     

The third industrial fluid properties simulation challenge

The third industrial fluid properties simulation challenge was held from March to September 2006. As in the previous two events contestants were challenged to predict specific, industrially relevant, properties of fluid systems. Their efforts were judged based on the agreement of the predicted values with previously unpublished experimental data (provided by researchers at ExxonMobil and DuPont). The focus of this contest was on the transferability of modeling methods—the ability to predict properties for materials that are chemically different, or at different state points, to those used in model parameterization and validation. Nine groups attempted to compute bubble point pressures for mixtures of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) and ethanol at 343 K, given data for mixtures at 283 K, and given the pure component vapor pressures. They used a range of different techniques including statistical mechanical and molecular simulations-based approaches. Four of the groups were recognized for providing predictions that were significantly more accurate than would be obtained by extrapolation using the NRTL model (the standard engineering approach). Three groups undertook the more challenging “molecular transferability” problem, attempting to predict shear viscosities at two different state points for a range of diols and triols for which little experimental data was available.     

The Institute for Operational Research: An Initiative to Extend the Scope of OR

One of the aims in forming the Institute for Operational Research (IOR) in 1963 was to expand the fields of application of OR and to reverse the tendency, then evident, for it to settle down as a mainly in-house, industrial activity deriving its strength from mathematics and the hard sciences, with little research content of its own. The paper outlines the early work done at IOR in pursuit of this mission, especially in multi-organizational settings such as city and regional planning, health services and the building industry. This leads into discussion of the conditions under which the work was done, the style of ‘action-research’ that evolved, its influence at the time, and its relevance to the different circumstances of the present day.     

Tuning interfacial charge-transfer excitons at polymer-polymer heterojunctions under hydrostatic pressure

We present photoluminescence spectroscopy of blend thin films of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) with electron-donating copolymers under hydrostatic pressure. The photoluminescence spectrum of F8BT redshifts by 530+/-60 meV over pressures of 0.1 MPa-8.8 GPa. That of the interfacial charge-transfer exciton redshifts by 270-370 meV over a similar pressure range. Despite the relatively small shift of the charge-transfer exciton, the excited state dynamics at the molecular heterojunction are strongly enhanced due to the decreasing intermolecular distance, leading to favored exciplex emission.     

Cover Picture: Supramolecular Self-Assembly as a Tool To Preserve the Electronic Purity of Perylene Diimide Chromophores (Angew. Chem. Int. Ed. 12/2023)

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.