The reaction of tetrachloroauric acid in DMF with poly(ethylene imine) (PEI) as a reducing agent yields spherical nanoparticles. Depending on the reaction conditions single gold nanoparticles or gold-PEI clusters with tunable size up to 200 nm in diameter were obtained which could serve as potential building blocks for metamaterials.

The unique properties of plasmonic nanostructures have fuelled research based on the tremendous amount of potential applications. Their tailor‐made assemblies in combination with the tunable size and morphology of the initial building blocks allow for the creation of materials with a desired optical response. In this respect, it is crucial to synthesize nanoparticles with a defined shape that are at the core of such developments. Moreover, the interaction of individual nanoparticles with an incident electromagnetic field cannot only be influenced by their structure, but in fact, also by their spatial arrangement to each other. To harvest such opportunities, a profound theoretical understanding of these interactions is required as well as concise strategies to create such ordered assemblies. A quantitative evaluation of their optical properties can only be conducted when discrete structures of high uniformity can be achieved. As a consequence, separation steps have to be applied in order to obtain materials of high purity and uniformity. This also allows for an easier structural characterization of the nanoparticles and their assembled superstructures. In this progress report, an overview about the current development in this field of research is provided.

Bonding individual metallic nanoparticles at small separation distances to let them form dimers and making them available in large quantities is a key requirement for various applications that wish to exploit the tremendous enhancement of electromagnetic fields in plasmonic junctions. Although progress has been witnessed in the past concerning the fabrication of dimers mediated by rigid molecular linkers, the exact bonding mechanism remains unclear.Here, we describe the fabrication of a rigid linker molecule and demonstrate its feasibility to achieve dimers made from closely spaced metallic nanoparticles in large quantities. Although the topography of the dimers proofs the success of the fabrication method, we use what we call a hypermethod characterization approach to study the optical properties of dimers from various perspectives. Measuring the surface enhanced Raman scattering signal of the linker molecule enables tracing directly the optical environment it perceives. By reaching a strong field enhancement in the gap of the dimers, we are able to investigate optical and geometrical properties of the linker. Moreover, upon isolation of the dimers, we use single particle extinction spectroscopy to study the optical response of a fabricated dimer directly. Full wave numerical simulations corroborate the experimental results and provide insights into quantities, which cannot be accessed directly in experiments. The ability to fabricate and to characterize rigidly linked nanoparticles will pave the way towards various plasmonic applications such as sensors, photocatalysis, and plexcitonics.

The influence of various polar solvent additives with different dipole moments has been investigated since the performance of a photovoltaic device comprising a donor-acceptor copolymer (benzothiadiazole-fluorene-diketopyrrolopyrrole (BTD-F-DKPP)) and phenyl-C60-butyric acid methyl ester (PCBM) was notably increased. A common approach for controlling bulk heterojunction morphology and thereby improving the solar cell performance involves the use of solvent additives exhibiting boiling points higher than that of the surrounding solvent in order to allow the fullerene to aggregate during the host solvent evaporation and film solidification. In contrast to that, we report the application of polar solvent additives with widely varied dipole moments, where intentionally no dependence on their boiling points was applied. We found that an appropriate amount of the additive can improve all solar cell parameters. This beneficial effect could be largely attributed to a modification of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-active layer interface within the device layer stack, which was successfully reproduced for polymer solar cells based on the commonly used PCDTBT (poly[N-900-hepta-decanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)]) copolymer.

Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross-linkable nanostructured materials via Diels-Alder reactions. Here, the use of FGE for the mid-chain functionalization of a P2VP-b-PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68 -FGE-b-PEO390 , which can be subsequently addressed in Diels-Alder reactions using maleimide-functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero-grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68 -FGE-b-PEO390 , a powerful tool for selective functionalization reactions, including the modification of surfaces.