Andreas Kunzmann

Designing dye-nanochannel antenna hybrid materials for light harvesting, transport and trapping.

We discuss artificial photonic antenna systems that are built by incorporating chromophores into one-dimensional nanochannel materials and by organizing the latter in specific ways. Zeolite L (ZL) is an excellent host for the supramolecular organization of different kinds of molecules and complexes. The range of possibilities for filling its one-dimensional channels with suitable guests has been shown to be much larger than one might expect. Geometrical constraints imposed by the host structure lead to supramolecular organization of the guests in the channels. The arrangement of dyes inside the ZL channels is what we call the first stage of organization. It allows light harvesting within the volume of a dye-loaded ZL crystal and also the radiationless transport of energy to either the channel ends or center. One-dimensional FRET transport can be realized in these guest-host materials. The second stage of organization is realized by coupling either an external acceptor or donor stopcock fluorophore at the ends of the ZL channels, which can then trap or inject electronic excitation energy. The third stage of organization is obtained by interfacing the material to an external device via a stopcock intermediate. A possibility to achieve higher levels of organization is by controlled assembly of the host into ordered structures and preparation of monodirectional materials. The usually strong light scattering of ZL can be suppressed by refractive-index matching and avoidance of microphase separation in hybrid polymer/dye-ZL materials. The concepts are illustrated and discussed in detail on a bidirectional dye antenna system. Experimental results of two materials with a donor-to-acceptor ratio of 33:1 and 52:1, respectively, and a three-dye system illustrate the validity and challenges of this approach for synthesizing dye-nanochannel hybrid materials for light harvesting, transport, and trapping.

The Yellow Color of Silver‐Containing Zeolite A

Not the Ag clusters, but rather the O atoms are responsible for the yellow color of silver-containing zeolite A. The reason for this has remained unclear since 1962. It is now shown that a charge-transfer transition from the lattice oxygen atoms to the empty 5s orbital of the silver ions (shown schematically on the right) is responsible for the yellow coloring.

Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis, Properties, and Composite Materials.

Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two- and three-color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure-transport relationship in ZL because their core fits tightly through the 12-ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long-term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye-ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye-zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics.

N -Heterotriangulene chromophores with 4-pyridyl anchors for dye-sensitized solar cells

A series of dimethylmethylene-bridged N-heterotriangulenes decorated with one, two, and three electron-withdrawing 4-pyridyls were synthesized. Their photophysical and electrochemical characteristics were examined and their successful application in n-type TiO2- and ZnO-based dye-sensitized solar cells demonstrated the ability of the 4-pyridyl moiety to act as an anchor.

Die gelbe Farbe von silberhaltigem Zeolith A

austauschen. Der im hydratisierten Zustand farblose Ag a Na aˇx-A- Zeolith ist nach der Aktivierung gelb bis ziegelrot. Ralek et al. stellten diese Farbver‰nderung erstmals nach thermi- scher Aktivierung im Vakuum fest. (2) Sie wurde sp‰ter von mehreren Autoren im Zusammenhang mit der Bildung von Silberclustern diskutiert. (3) Postuliert wurde ein Autoreduk- tionsmechanismus unter Bildung von Ag 0 -Zentren und Frei- setzung von O2 aus dem Zeolithgerst. Wir zeigen, das die Hochvakuumaktivierung schon bei Raumtemperatur zu gel- bem Silber-A-Zeolith fhrt und das alle im UV/Vis-Bereich auftretenden Absorptionsbanden nur von der Hydratation der Silberionen abh‰ngen. Wir erkl‰ren die gelbe Farbe mit elektronischen ‹berg‰ngen von den freien Elektronenpaaren der Sauerstoffatome des Zeolithgersts auf leere 5s-Orbitale von Ag a -Ionen (ligand to metal charge transfer, LMCT).

Singlet Fission for Photovoltaics with 130 % Injection Efficiency

A novel pentacene dimer (P2) and a structurally analogous monomer (P1) were synthesized for use in n-type dye-sensitized solar cells. In P2, the triplet excited states formed by the rapid, spin-allowed process singlet fission were expected to enable carrier multiplication in comparison to the slow, spin-forbidden intersystem crossing seen in P1. A meta-positioning of the two pentacenes and the carboxylate anchor were chosen in P2 to balance the intramolecular dynamics of singlet fission and electron injection. Electron injection from energetically low-lying triplet excited states of pentacene units necessitated the intrinsic and extrinsic lowering of the Fermi level of the semiconductor. Indium-zinc oxide in the presence of Li+ was found to be the optimum choice for the photoelectrodes. Efficient electron injection from the triplet excited states of P1 and P2 was found, with a carrier multiplication of nearly 130 %.

Choosing the right nanoparticle size – designing novel ZnO electrode architectures for efficient dye-sensitized solar cells

A novel concept for constructing optimized ZnO-based photoanodes as integrative components of dye-sensitized solar cells (DSSCs) is realized by deploying differently sized nanoparticles, ranging from 2 to 10 nm, together with commercially available 20 nm nanoparticles. The 2 nm nanoparticles were used to construct an efficient buffer layer for transparent electrodes based on 10 nm nanoparticles, resulting in a relative increase of device efficiency from 1.8 to 3.0% for devices without and with a buffer layer, respectively. A mixture of 10 and 20 nm nanoparticles was optimized to maximize the diffuse reflection and to minimize the charge transport resistance in a light-scattering layer. This optimization resulted in a homogenous layer of more than 15 μm that provided a device efficiency of 3.3%. The buffer layer, transparent electrode, and light-scattering electrode, were then combined to give an overall efficiency of around 5%. Thus, this work demonstrates that varying the electrode architecture with nanoparticles of different diameters is a powerful strategy for improving the overall efficiency of ZnO-based DSSCs.

Synergy of Catechol-Functionalized Zinc Oxide Nanorods and Porphyrins in Layer-by-Layer Assemblies

Catechol-functionalized, positively charged ZnO nanorods (NRs) and anionic porphyrins were integrated into layer-by-layer (LbL) assemblies. In general, this study focuses on the impact that different porphyrins, varying in size and number of negative charges, exert on the LbL architecture in terms of morphology and spectroscopy. In particular, through a combination of analytical methods, including UV/Vis spectroscopy, SEM, and profilometry, valuable insights into LbL assembly formation were gathered. A key feature was the surface coverage in the resulting films. Denser films and surface coverages were realized when highly negatively charged and sterically demanding porphyrins were employed. As a complement to basic characterization, the LbL assembled films were used to fabricate proof-of-concept solar cells.