TY - JOUR A1 - Heinrich, Thomas A1 - Traulsen, Christoph Hans-Henning A1 - Darlatt, Erik A1 - Richter, S. A1 - Poppenberg, J. A1 - Traulsen, N.L. A1 - Linder, I. A1 - Lippitz, Andreas A1 - Dietrich, Paul A1 - Dib, B. A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - The versatility of 'Click' reactions at surfaces: Molecular recognition at interfaces N2 - In order to investigate molecular recognition on surfaces, an azide-functionalized monolayer was deposited on gold. The monolayer was characterized by X-ray photoelectron spectroscopy (XPS) and angle-resolved near-edge X-ray absorption fine structure (NEXAFS) experiments and the decomposition of the azide upon irradiation with X-ray beams was investigated. Subsequently, various alkyne-functionalized host and guest molecules were attached to the azide by 1,3-dipolar cycloaddition. These modified surfaces and their host–guest chemistry were analysed by XPS and angle-resolved NEXAFS. The reversibility of guest binding was shown for one example as a proof of principle. KW - 'Click' reaction KW - Azide-terminated surfaces KW - SAMs KW - Host guest molecules KW - Molecular recognition at interfaces PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-306463 DO - https://doi.org/10.1039/C4RA01730G SN - 2046-2069 VL - 4 IS - 34 SP - 17694 EP - 17702 PB - RSC Publishing CY - London AN - OPUS4-30646 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heinrich, Thomas A1 - Traulsen, Christoph Hans-Henning A1 - Holzweber, Markus A1 - Richter, S. A1 - Kunz, V. A1 - Kastner, S.K. A1 - Krabbenborg, S.O. A1 - Huskens, J. A1 - Unger, Wolfgang A1 - Schalley, C.A. T1 - Coupled molecular switching processes in ordered mono- and multilayers of stimulus-responsive rotaxanes on gold surfaces N2 - Interfaces provide the structural basis for function as, for example, encountered in nature in the membrane-embedded photosystem or in technology in solar cells. Synthetic functional multilayers of molecules cooperating in a coupled manner can be fabricated on surfaces through layer-by-layer self-assembly. Ordered arrays of stimulus-responsive rotaxanes undergoing well-controlled axle shuttling are excellent candidates for coupled mechanical motion. Such stimulus-responsive surfaces may help integrate synthetic molecular machines in larger systems exhibiting even macroscopic effects or generating mechanical work from chemical energy through cooperative action. The present work demonstrates the successful deposition of ordered mono- and multilayers of chemically switchable rotaxanes on gold surfaces. Rotaxane mono- and multilayers are shown to reversibly switch in a coupled manner between two ordered states as revealed by linear dichroism effects in angle-resolved NEXAFS spectra. Such a concerted switching process is observed only when the surfaces are well packed, while less densely packed surfaces lacking lateral order do not exhibit such effects. KW - Molecular machine KW - Rotaxane KW - LBL growth KW - XPS KW - NEXAFS KW - SIMS PY - 2015 DO - https://doi.org/10.1021/ja512654d SN - 0002-7863 SN - 1520-5126 VL - 137 IS - 13 SP - 4382 EP - 4390 PB - American Chemical Society CY - Washington, DC, USA AN - OPUS4-33077 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Traulsen, Christoph T1 - Programmierbare supramolekulare (Komposit-)Multischichten auf Gold- und Siliziumoberflächen N2 - The present doctoral thesis focuses on the deposition of programmable supramolecular multilayers and composite-multilayers on gold and silicon substrates using a layer-by-layer selfassembly approach which is based on coordination chemistry. For this purpose, a variety of pyridine- and terpyridine-terminated self-assembled monolayers has been developed and deposited on gold and silicon substrates. Multitechnique analysis was carried out using X-ray photoelectron spectroscopy (XPS), (angle-dependent) near-edge Xray-absorption fine-structure spectroscopy (NEXAFS spectroscopy), time-of-flight secondaryion mass spectrometry (ToF-SIMS), transmissions UV/Vis spectroscopy as well as atomic force microscopy (AFM). By optimization of the deposition procedure, highly-ordered monomolecular and binary monolayers were deposited. As a proof of principle, transition metal-ions and appropriately labeled test-ligands were deposited on top of the functional monolayers. Furthermore, monolayers of terpyridine-terminated tetralactam macrocycles and the corresponding ether rotaxanes have been immobilized using coordination chemistry. In order to enhance the macrocycle surface coverage, the deposition procedure has been optimized as well. Multilayers consisting of diterpyridine-terminated tetralactam macrocycles have been deposited using either Fe(II) or alternatingly Fe(II) and Ni(II) metal-ions. The surface analysis proved a regular layer growth and a remarkable orientation of the macrocycles within the layer stacks. The applicability of the deposition procedure was expanded to a programmable layer stack by implementing pyridine-terminated macrocycles. The monodentate ligands led to an additional coordination sphere and thus to the application of a different transition metal-ion. The macrocycles and metal-ions were programmed according to the deposition sequence applied. The corresponding layer stack exhibited a linear dichroism of the π*-resonance corresponding to a preferential orientation of the macrocycles. Furthermore, the concept was extended to the deposition of composite multilayers consisting of pyridine-functionalized macrocycles and gold-nanoparticles which were synthesized during this thesis as well. Finally, reversible on-surface host-guest complex formation N2 - Die vorliegende Dissertation befasst sich mit der Herstellung von programmierbaren, supramolekularen Multischichten und Komposit-Multischichten auf Gold- und Siliziumoberflächen durch Anwendung eines koordinationschemischen Schicht-auf-Schicht-Selbstorganisationsverfahrens und den damit verbundenen Synthesen, Beschichtungen und Analysen. Um dieses Ziel zu erreichen, wurde zunächst eine Vielzahl von pyridin- und terpyridinterminierten selbstorganisierten Monoschichten (SAM) hergestellt und auf Gold- und Siliziumoberflächen abgeschieden. Die Abscheideprozedur wurde optimiert wobei zur Analytik der Oberflächen Röntgenphotoelektronenspektroskopie (XPS), winkelabhängiger kantennaher Röntgenabsorptionsfeinstrukturspektroskopie (NEXAFS-Spektroskopie), Flugzeit-Sekundärionen-Massenspektrometrie (ToF-SIMS), Transmissions-UV/Vis-Spektroskopie sowie Rasterkraftmikroskopie (AFM) eingesetzt wurde. Es konnte gezeigt werden, dass sich hochgeordnete monomolekulare und gemischte Monoschichten erzeugen lassen. Die terminalen funktionellen Gruppen dieser SAMs konnten als Ligand zur Komplexbildung mit Übergangsmetallionen verwendet werden. Diese koordinative Haftschicht wurde zur Verknüpfung zunächst von Testliganden und später von terpyridin-terminierten Tetralactam-Makrozyklen (TLM) und darauf basierenden Etherrotaxanen verwendet. Hierbei wurden ebenfalls die Beschichtungsbedingungen optimiert, um einen vollständigen Bedeckungsgrad zu erreichen. Unter Verwendung dieser Bedingungen wurden anschließend Multischichten aus TLMs und Fe(II)-Ionen sowie alternierend Fe(II) und Ni(II) abgeschieden. Die Analyse der hergestellten Multischichten zeigte reproduzierbar ein regelmäßiges, kontrollierbares Wachstum und eine Vorzugsorientierung. Durch den Einsatz von pyridin- und terpyridin-terminierten TLMs mit variierenden Metallionen konnte gezeigt werden, dass es möglich ist, die Abfolge verschiedener Schichten der Multischicht gezielt festzulegen. Im weiteren Verlauf der Arbeit wurden pyridin-terminierte Goldnanopartikel hergestellt und in die Multischichten integriert, um so Komposit-Multischichten herzustellen. Letztlich konnte gezeigt werden, dass die erzeugten Multischichten genutzt werden können, um über nicht-kovalente Wechselwirkungen reversibel Gastmoleküle zu binden und freizusetzten. KW - Layer-by-layer deposition KW - XPS KW - NEXAFS KW - ToF SIMS KW - Progammable rotaxane stacks PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:188-fudissthesis000000096664-6 SP - 1 EP - 141 PB - Freie Universität CY - Berlin AN - OPUS4-39615 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -