Exciton bimolecular annihilation dynamics in supramolecular nanostructures of conjugated oligomers

We present femtosecond transient absorption measurements on $\pi$-conjugated supramolecular assemblies in a high pump fluence regime. Oligo(\emph{p}-phenylenevinylene) monofunctionalized with ureido-\emph{s}-triazine (MOPV) self-assembles into chiral stacks in dodecane solution below 75$^{\circ}$C at a concentration of $4\times 10^{-4}$ M. We observe exciton bimolecular annihilation in MOPV stacks at high excitation fluence, indicated by the fluence-dependent decay of $1^1$B$_{u}$-exciton spectral signatures, and by the sub-linear fluence dependence of time- and wavelength-integrated photoluminescence (PL) intensity. These two characteristics are much less pronounced in MOPV solution where the phase equilibrium is shifted significantly away from supramolecular assembly, slightly below the transition temperature. A mesoscopic rate-equation model is applied to extract the bimolecular annihilation rate constant from the excitation fluence dependence of transient absorption and PL signals. The results demonstrate that the bimolecular annihilation rate is very high with a square-root dependence in time. The exciton annihilation results from a combination of fast exciton diffusion and resonance energy transfer. The supramolecular nanostructures studied here have electronic properties that are intermediate between molecular aggregates and polymeric semiconductors

Spatial layout planning in sub-surface rail station design for effective fire evacuation

The London Underground network is a crucial part of the transportation system in one of only four ‘Alpha’ world cities. The other three – Paris, New York and Tokyo – also have such sub-surface railway transport systems that may benefit from this shape grammar station design process in a future research proposal. In London’s case, the passenger flow rates are the underlining factor in sizing infrastructure where passengers have access – it is therefore this criterion that provides the basis for the shape grammar formulation for the largest, oldest and one of the most complex underground systems in the world. The research aims to improve passenger fire evacuation times, with due cognisance of the growth of numbers using the system, and its present susceptibility to terrorist attacks taken into account. The proposed shape grammar approach will provide for generation of spatial layouts, based upon visual rules of shape recognition, replacement / union, their connectivity and spatial relationships. The paper concentrates on definition and implementation of novel shape grammar design rules that incorporate station planning design knowledge, and in particular also discusses designers’ fire risk assessment approach and related knowledge that is also needed to produce credible station design solutions. Development, to date, of the proposed artificially intelligent CAD environment is also described along with parallel theoretical research. The proposed CAD interface provides familiarity to the designer and avoids incompatibility issues regarding drawing exchange format between various software systems. The shape grammar layouts produced will be tested in SIMULEX, a commercially available evacuation package, and be compared against ‘traditionally’ designed layouts to demonstrate improvements of preliminary ‘reference’ designs, which follow the standard London Underground design process as a later stage of this research

Beyond the Woodward-Hoffman rules: what controls reactivity in eliminative aromatic ring-forming reactions?

The Mallory (photocyclization) and Scholl (thermal cyclohydrogenation) reactions are widely used in the synthesis of extended conjugated π systems of high scientific interest and technological importance, including molecular wires, semiconducting polymers and nanographenes. While simple electrocyclization reactions obey the Woodward-Hoffman rules, no such simple, general and powerful model is available for eliminative cyclization reactions due to their increased mechanistic complexity. In this work, detailed mechanistic investigations of prototypical reactions reveal that there is no single rate-determining step for thermal oxidative dehydrogenation reactions, but they are very sensitive to the presence and distribution of heteroatoms around the photocyclizing ring system. Key aspects of reactivity are correlated to the constituent ring oxidation potentials. For photocyclization reactions, planarization occurs readily and/or spontaneously following photo-excitation, and is promoted by heteroatoms within 5-membered ring adjacent to the photocyclizing site. Oxidative photocyclization requires intersystem crossing to proceed to products, while reactants configured to undergo purely eliminative photocyclization could proceed to products entirely in the excited state. Overall, oxidative photocyclization seems to strike the optimal balance between synthetic convenience (ease of preparation of reactants, mild conditions, tolerant to chemical diversity in reactants) and favourable kinetic and thermodynamic properties