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An amphiphilic phosphodiester-linked azobenzene trimer has been exploited in the development of stimuli-responsive, water-soluble supramolecular polymers. The trimer can reversibly undergo thermal and photoisomerization between Z- and E-isomers. Its self-assembly properties in aqueous medium have been investigated by spectroscopic and microscopic techniques, demonstrating that E- and Z-azobenzene trimers form supramolecular nanosheets and toroidal nanostructures, respectively. By virtue of the E/Z photoisomerization of the azobenzene units, the two different supramolecular morphologies can be switched by photoirradiation. The findings pave a way towards stimuli-responsive, water-soluble supramolecular polymers which hold great promise in the development of smart functional materials., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Nitrogen-doped Kagome graphene (N-KG) has been theoretically predicted as a candidate for the emergence of a topological band gap as well as unconventional superconductivity. However, its physical realization still remains very elusive. Here, we report on a substrate-assisted reaction on Ag(111) for the synthesis of two-dimensional graphene sheets possessing a long-range honeycomb Kagome lattice. Low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) with a CO-terminated tip supported by density functional theory (DFT) are employed to scrutinize the structural and electronic properties of the N-KG down to the atomic scale. We demonstrate its semiconducting character due to the nitrogen doping as well as the emergence of Kagome flat bands near the Fermi level which would open new routes towards the design of graphene-based topological materials., (© 2021 Wiley-VCH GmbH.)

An approach combining DNA nanoscaffolds with supramolecular polymers for the efficient and directional propagation of light-harvesting cascades has been developed. A series of photonic wires with different arrangements of fluorophores in DNA-organized nanostructures were linked to light-harvesting supramolecular phenanthrene polymers (SPs) in a self-assembled fashion. Among them, a light-harvesting complex (LHC) composed of SPs and a photonic wire of phenanthrene, Cy3, Cy5, and Cy5.5 chromophores reveals a remarkable energy transfer efficiency of 59 %. Stepwise transfer of the excitation energy collected by the light-harvesting SPs via the intermediate Cy3 and Cy5 chromophores to the final Cy5.5 acceptor proceeds through a Förster resonance energy transfer mechanism. In addition, the light-harvesting properties are documented by antenna effects ranging from 1.4 up to 23 for different LHCs., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite a growing interest in two-dimensional polymers, their rational synthesis remains a challenge. The solution-phase synthesis of a two-dimensional polymer is reported. A DNA-based monomer self-assembles into a supramolecular network, which is further converted into the covalently linked two-dimensional polymer by anthracene dimerization. The polymers appear as uniform monolayers, as shown by AFM and TEM imaging. Furthermore, they exhibit a pronounced solvent responsivity. The results demonstrate the value of DNA-controlled self-assembly for the formation of two-dimensional polymers in solution., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A 2,7-disubstituted phosphodiester-linked phenanthrene trimer forms tubular structures in aqueous media. Chromophores are arranged in H-aggregates. Incorporation of small quantities of pyrene results in the development of light-harvesting nanotubes in which phenanthrenes act as antenna chromophores and pyrenes as energy acceptors. Energy collection is most efficient after excitation at the phenanthrene H-band. Fluorescence quantum yields up to 23 % are reached in pyrene doped, supramolecular nanotubes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The controlled arraying of DNA strands on adaptive polymeric platforms remains a challenge. Here, the noncovalent synthesis of DNA-grafted supramolecular polymers from short chimeric oligomers is presented. The oligomers are composed of an oligopyrenotide strand attached to the 5'-end of an oligodeoxynucleotide. The supramolecular polymerization of these oligomers in an aqueous medium leads to the formation of one-dimensional (1D) helical ribbon structures. Atomic force and transmission electron microscopy show rod-like polymers of several hundred nanometers in length. DNA-grafted polymers of the type described herein will serve as models for the development of structurally and functionally diverse supramolecular platforms with applications in materials science and diagnostics., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The understanding and description of collectively excited multichromophores is of crucial importance for many areas of basic and applied research. DNA has been used for the construction of well-defined heterochromophoric stacks. Electronic coupling among non-adjacent chromophores of the same type leads to the co-existence of PDI and pyrene H-aggregates in hybrids composed of alternating chromophore stacks., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The efficient collection of solar energy relies on the design and construction of well-organized light-harvesting systems. Herein we report that supramolecular phenanthrene polymers doped with pyrene are effective collectors of light energy. The linear polymers are formed through the assembly of short amphiphilic oligomers in water. Absorption of light by phenanthrene residues is followed by electronic energy transfer along the polymer over long distances (>100 nm) to the accepting pyrene molecules. The high efficiency of the energy transfer, which is documented by large fluorescence quantum yields, suggests a quantum coherent process., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Reading the bands: Amphiphilic pyrene trimers self-assemble into two-dimensional, supramolecular polymers in aqueous medium. Folding and aggregation processes are accompanied by simultaneous development of J- and H-bands and significant changes in the fluorescence properties. The formation of sheet-like nano-structures is confirmed by AFM., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Getting organized: DNA-like supramolecular polymers formed of short oligopyrenotides serve as a helical scaffold for the molecular assembly of ligands. The cationic porphyrin meso-tetrakis(1-methylpyridin-4-yl)porphyrin interacts with the helical polymers in a similar way as with poly(dA:dT)., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)