BEST POSTER AWARD received by Anika Joest
We proudly congratulate Anika Joest on receiving the Best Poster Award at this year’s European Symposium on Organic Chemistry (ESOC 2025) in Copenhagen. Her poster was selected by the scientific committee for its innovative approach to the regio- and stereoselective synthesis of polypropionate building blocks – a method that enables the preparation of the archetypal stereotriad of the important natural products from a single achiral substrate.
Plasmon mediated coherent population oscillations in molecular aggregates
The strong coherent coupling of quantum emitters to vacuum fluctuations of the light field offers opportunities for manipulating the optical and transport properties of nanomaterials, with potential applications ranging from ultrasensitive all-optical switching to creating polariton condensates.
Modular Bicyclophane-Based Molecular Platforms
Bicyclophane-based molecular platforms form extended 2D crystalline monolayers after adsorption from solution onto HOPG and contain orthogonal pillars that point towards the supernatant solution phase.
Nanoscale π-conjugated ladders
It is challenging to increase the rigidity of a macromolecule while maintaining solubility. Established strategies rely on templating by dendrons, or by encapsulation in macrocycles, and exploit supramolecular arrangements with limited robustness. Covalently bonded structures have entailed intramolecular coupling of units to resemble the structure of an alternating tread ladder with rungs composed of a covalent bond. We introduce a versatile concept of rigidification in which two rigid-rod polymer chains are repeatedly covalently associated along their contour by stiff molecular connectors. This approach yields almost perfect ladder structures with two well-defined π-conjugated rails and discretely spaced nanoscale rungs, easily visualized by scanning tunnelling microscopy. The enhancement of molecular rigidity is confirmed by the fluorescence depolarization dynamics and complemented by molecular-dynamics simulations. The covalent templating of the rods leads to self-rigidification that gives rise to intramolecular electronic coupling, enhancing excitonic coherence. The molecules are characterized by unprecedented excitonic mobility, giving rise to excitonic interactions on length scales exceeding 100 nm. Such interactions lead to deterministic single-photon emission from these giant rigid macromolecules, with potential implications for energy conversion in optoelectronic devices.
Subcomponent self-assembly of circular helical Dy6(L)6 and bipyramid Dy12(L)8 architectures
Subcomponent self-assembly gave access to Dy12(L)8 and Dy6(L)6 architectures via second-order template effects. The Dy6(L)6 assembly behaves as a single-molecule magnet exhibiting a high anisotropy barrier and butterfly-shaped magnetic hysteresis.
Structural Disorder as the Origin of Optical Properties and Spectral Dynamics in Squaraine Nano-Aggregates
In contrast to regular J- and H-aggregates, thin film squaraine aggregates usually have broad absorption spectra containing both J-and H-like features, which are favorable for organic photovoltaics. Despite being successfully applied in organic photovoltaics for years, a clear interpretation of these optical properties by relating them to specific excited states and an underlying aggregate structure has not been made. In this work, by static and transient absorption spectroscopy on aggregated n-butyl anilino squaraines, we provide evidence that both the red- and blue-shifted peaks can be explained by assuming an ensemble of aggregates with intermolecular dipole–dipole resonance interactions and structural disorder deriving from the four different nearest neighbor alignments - in sharp contrast to previous association of the peaks with intermolecular charge-transfer interactions. In our model, the next-nearest neighbor dipole-dipole interactions may be negative or positive, which leads to the occurrence of J- and H-like features in the absorption spectrum. Upon femtosecond pulse excitation of the aggregated sample, a transient absorption spectrum deviating from the absorbance spectrum emerges. The deviation finds its origin in the excitation of two-exciton states by the probe pulse. The lifetime of the exciton is confirmed by the band integral dynamics, featuring a single-exponential decay with a lifetime of 205 ps. Our results disclose the aggregated structure and the origin of red- and blue-shifted peaks and explain the absence of photoluminescence in squaraine thin films. Our findings underline the important role of structural disorder of molecular aggregates for photovoltaic applications.
A family of heterobimetallic cubes shows spin-crossover behaviour near room temperature
Starting from simple building blocks, six heterobimetallic cubes were obtained, following a straight-forward subcomponent self-assembly strategy. Three iron(II) based cages showed spin-crossover behaviour in solution. The crossover temperature was strongly dependent on interchangeable aldehyde components, giving rise to an efficient toolkit to manipulate magnetic behaviour.
Charge Delocalization and Vibronic Couplings in Quadrupolar Squaraine Dyes
Squaraines are prototypical quadrupolar charge-transfer chromophores that have recently attracted much attention as building blocks for solution-processed photovoltaics, fluorescent probes with large two-photon absorption cross sections, and aggregates with large circular dichroism. Their optical properties are often rationalized in terms of phenomenological essential state models, considering the coupling of two zwitterionic excited states to a neutral ground state. As a result, optical transitions to the lowest S1 excited state are one-photon allowed, whereas the next higher S2 state can only be accessed by two-photon transitions. A further implication of these models is a substantial reduction of vibronic coupling to the ubiquitous high-frequency vinyl-stretching modes of organic materials. Here, we combine time-resolved vibrational spectroscopy, two-dimensional electronic spectroscopy, and quantum-chemical simulations to test and rationalize these predictions for non-aggregated molecules. We find small Huang–Rhys factors below 0.01 for the high-frequency, 1500 cm–1 modes in particular, as well as a noticeable reduction for those of lower frequency modes in general for the electronic S0 → S1 transition. The two-photon allowed state S2 is well separated energetically from S1 and has weak vibronic signatures as well. Thus, the resulting pronounced concentration of the oscillator strength in a narrow region relevant to the lowest electronic transition makes squaraines and their aggregates exceptionally interesting for strong and ultrastrong coupling of excitons to localized light modes in external resonators with chiral properties that can largely be controlled by the molecular architecture.