Approaching the Integer-Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross-Coupling

A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross-coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross-coupling partners without the need of co-catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.     

Impact of Positional Isomerism on Pathway Complexity in Aqueous Media

Pathway complexity has become an important topic in recent years due to its relevance in the optimization of molecular assembly processes, which typically require precise sample preparation protocols. Alternatively, competing aggregation pathways can be controlled by molecular design, which primarily rely on geometrical changes of the building blocks. However, understanding how to control pathway complexity by molecular design remains elusive and new approaches are needed. Herein, we exploit positional isomerism as a new molecular design strategy for pathway control in aqueous self‐assembly. We compare the self‐assembly of two carboxyl‐functionalized amphiphilic BODIPY dyes that solely differ in the relative position of functional groups. Placement of the carboxyl group at the 2‐position enables efficient pairwise H‐bonding interactions into a single thermodynamic species, whereas meso‐substitution induces pathway complexity due to competing hydrophobic and hydrogen bonding interactions. Our results show the importance of positional engineering for pathway control in aqueous self‐assembly.     

A Monoidal Category for Perturbed Defects in Conformal Field Theory

Starting from an abelian rigid braided monoidal category C{\mathcal{C}} we define an abelian rigid monoidal category C_F{\mathcal{C}_F} which captures some aspects of perturbed conformal defects in two-dimensional conformal field theory. Namely, for V a rational vertex operator algebra we consider the charge-conjugation CFT constructed from V (the Cardy case). Then C = Rep(V){\mathcal{C} = {\rm Rep}(V)} and an object in C_F{\mathcal{C}_F} corresponds to a conformal defect condition together with a direction of perturbation. We assign to each object in C_F{\mathcal{C}_F} an operator on the space of states of the CFT, the perturbed defect operator, and show that the assignment factors through the Grothendieck ring of C_F{\mathcal{C}_F}. This allows one to find functional relations between perturbed defect operators. Such relations are interesting because they contain information about the integrable structure of the CFT.     

Metric entropy of convex hulls in type spaces--The critical case

Given a precompact subset of a type Banach space , where , we prove that for every and all

holds, where is the absolutely convex hull of and denotes the dyadic entropy number. With this inequality we show in particular that for given and with for all the inequality holds true for all . We also prove that this estimate is asymptotically optimal whenever has no better type than . For this answers a question raised by Carl, Kyrezi, and Pajor which has been solved up to now only for the Hilbert space case by F. Gao.

     

Synchronization of chaotic semiconductor laser systems: a vectorial coupling-dependent scenario

We demonstrate the influence of vectorial coupling on the synchronization behavior of complex systems. We study two semiconductor lasers subject to delayed optical feedback which are unidirectionally coherently coupled via their optical fields. Our experimental and numerical results demonstrate a characteristic synchronization scenario in dependence on the relative feedback phase leading cyclically from chaos synchronization to almost uncorrelated states, and back to chaos synchronization. Finally, we reveal the influence of the feedback phase on the dynamics of the solitary delay system.