Enhancing Long-Range Energy Transport in Supramolecular Architectures by Tailoring Coherence Properties

Efficient long-range energy transport along supramolecular architectures of functional organic molecules is a key step in nature for converting sunlight into a useful form of energy. Understanding and manipulating these transport processes on a molecular and supramolecular scale is a long-standing goal. However, the realization of a well-defined system that allows for tuning morphology and electronic properties as well as for resolution of transport in space and time is challenging. Here we show how the excited-state energy landscape and thus the coherence characteristics of electronic excitations can be modified by the hierarchical level of H-type supramolecular architectures. We visualize, at room temperature, long-range incoherent transport of delocalized singlet excitons on pico- to nanosecond time scales in single supramolecular nanofibers and bundles of nanofibers. Increasing the degree of coherence, i.e., exciton delocalization, via supramolecular architectures enhances exciton diffusivities up to 1 order of magnitude. In particular, we find that single supramolecular nanofibers exhibit the highest diffusivities reported for H-aggregates so far

Highly circularly polarized broad-band emission from chiral naphthalene diimide-based supramolecular aggregates

We report off-white circularly polarized luminescence (CPL) from supramolecular aggregates formed by a chiral carboxylic acid-functionalized naphthalene diimide. The self-assembly behaviour and the stability of the aggregates in solution were assessed by variable-temperature UV-Vis and electronic circular dichroism experiments. The observed 200 nm-wide emission band is unusual for a single chromophore and is a consequence of the supramolecular ordering due to a combination of π-stacking and H-bonding interactions, leading to excimer formation. High emission anisotropy factors glum, around |1-2| × 10-2, were observed over the whole spectrum in chlorinated/hydrocarbon solvent mixtures, as well as in thin films. These values are one order of magnitude higher than those of most chiral self-assembled fluorophores and other common small organic emitters

Switchable Charge Injection Barrier in an Organic Supramolecular Semiconductor

We disclose a supramolecular material that combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core, which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar fashion through π-stacking of the molecular core and hydrogen bonding between the amide groups. Alignment by an electrical field in a simple metal/semiconductor/metal geometry induces a polar order in the interface layers near the metal contacts that can be reversibly switched, while the bulk material remains nonpolarized. On suitably chosen electrodes, the presence of an interfacial polarization field leads to a modulation of the barrier for charge injection into the semiconductor. Consequently, a reversible switching is possible between a high-resistance, injection-limited off-state and a low-resistance, space-charge-limited on-state. The resulting memory diode shows switchable rectification with on/off ratios of up to two orders of magnitude. This demonstrated multifunctionality of a single material is a promising concept toward possible application in low-cost, large-area, nonvolatile organic memories.status: publishe

Pathway Complexity in the Enantioselective Self-Assembly of Functional Carbonyl-Bridged Triarylamine Trisamides

Functional supramolecular systems like carbonyl-bridged triarylamine (CBT) trisamides are known for their long-range energy transport at room temperature. Understanding the complex self-assembly processes of this system allows for control over generated structures using controlled supramolecular polymerization. Here, we present two novel CBT trisamides with (<i>S</i>)- or (<i>R</i>)-chiral side chains which show a two-pathway self-assembly behavior in solution. Depending on the thermal profile during the self-assembly process, two different stable states are obtained under otherwise identical conditions. A kinetically trapped state <b>A</b> is reached upon cooling to 7 °C, via a proposed isodesmic process. In addition, there is a thermodynamically stable state <b>B</b> at 7 °C that is induced by first undercooling to −5 °C, via a nucleation-elongation mechanism. In both cases, helical supramolecular aggregates comprising H-aggregated CBTs are formed. Additionally, controlled supramolecular polymerization was achieved by mixing the two different states (<b>A</b> and <b>B</b>) from the same enantiomer, leading to a conversion of the kinetically trapped state to the thermodynamically stable state. This process is highly enantioselective, as no conversion is observed if the two states consist of opposite enantiomers. We thus show the importance and opportunities emerging from understanding the pathway complexity of functional supramolecular systems

Switchable Charge Injection Barrier in an Organic Supramolecular Semiconductor

We disclose a supramolecular material that combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core, which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar fashion through Jr-stacking of the molecular core and hydrogen bonding between the amide groups. Alignment by an electrical field in a simple metal/semiconductor/metal geometry induces a polar order in the interface layers near the metal contacts that can be reversibly switched, while the bulk material remains nonpolarized. On suitably chosen electrodes, the presence of an interfacial polarization field leads to a modulation of the barrier for charge injection into the semiconductor. Consequently, a reversible switching is possible between a high-resistance, injection-limited off-state and a low-resistance, space-charge-limited on-state. The resulting memory diode shows switchable rectification with on/off ratios of up to two orders of magnitude. This demonstrated multifunctionality of a single material is a promising concept toward possible application in lowcost, large-area, nonvolatile organic memories.Funding Agencies|NWO Nano program; Bavarian State Ministry of Science, Research, and the Arts for the Collaborative Research Network Solar Technologies go Hybrid; Deutsche Forschungsgemeinschaft (DFG) [SFB 953]; Vetenskapsradet [2015-03813]</p