Photoschaltbare Azobenzol-modifizierte selbstorganisierte Monoschichten auf Gold(111)-Oberflächen

Für die Entwicklung photoschaltbarer selbstorganisierter Monoschichten (SAMs) auf Gold(111)-Oberflächen wurden neue Azobenzol-terminierte Asparagussäure - und Liponsäurederivate synthetisiert. Um den Einfluss lateraler Wasserstoffbrückenbindungen auf Qualität und Orientierungsordnung der Schichten zu untersuchen, wurden Monolagen, die durch amid- und esterverknüpfte Verbindungen gebildet wurden, miteinander verglichen. Die Filmbildung aus der Lösung wurde in situ durch optische Frequenzverdopplung (SHG) untersucht und die Photoreaktivität mittels Kontaktwinkelmessungen, Oberflächen-Plasmonenresonanz (SPR) und Ellipsometrie verfolgt. SAMs auf Gold wurden außerdem mit Hilfe von Röntgenphotoelektronenspektroskopie (XPS), Nahkanten-Reflexions-Röntgenabsorptionsspektroskopie (NEXAFS) und Infrarot-Reflexionsabsorptionsspektroskopie (IRRAS) charakterisiert, um die Filmqualität, die Bindung ans Substrat und Orientierungsordnung im Film zu ermitteln. Da die Chemisorption auf polykristallinem Gold formal der Koordinationschemie von 1,2-Dithiolan-Derivaten gegenüber nullwertigen Edelmetall-Zentralatomen entspricht, wurden etliche Pt-Komplexe durch oxidative Addition an [Pt(PPh3)4] dargestellt. Im Zusammenhang mit der Darstellung der Asparagussäure wurde die Kristallstruktur von [pipH]2[WS4] und der neuen Verbindungen [pipH]3[WS4](HS) und [pipH]4[WS4][WOS3] (pip = Piperidin) bestimmt. Wasserstoffbrückenbindungen zwischen den Piperidinium-Kationen und den Thiowolframat-Anionen spielen eine dominante strukturelle Rolle.

Synthese von Azobenzolderivaten zur Darstellung photoschaltbarer, selbstorganisierter Monolagen

Im Vordergrund dieser Arbeit stehen die Synthesen des Azobenzol-4-trichlorsilans sowie des Bis(4-azobenzol)disulfids, ausgehend von einfachen und kommerziell erhältlichen Verbindungen. Moleküle, aus denen sich diese Verbindungen synthetisieren lassen, sind die Iodderivate des Azobenzols, welche über die Kondensation von Benzolaminen (Anilinen) und Nitrosobenzolen dargestellt wurden, aber auch über die altbewährte Azokupplung. Insgesamt wurden 19 neue Azobenzolderivate, das neue [(4-Aminophenyl)ethinyl]ferrocen und das neue Bis[4-(4'-bromazobenzol)]disulfid synthetisiert und charakterisiert. Außerdem wurden 13 neue Kristallstrukturen erzeugt. Mit den synthetisierten Molekülen wurden Substrat-Adsorbat-Systeme gebildet. Als Substrate wurden oberflächenoxidiertes Silizium und Gold gewählt. Die Präparation dieser sogennanten selbstorganisierten Monolagen (SAMs) bzw. der kovalent gebundenen Monolagen im Falle der Trichlorsilylderivate (CAMs) wurde eingehend studiert. Das Azobenzol wurde als photoschaltbare Einheit gewählt, da es bereits Kern zahlreicher Untersuchungen war und als solcher als guter und zuverlässiger Baustein für reversible photoschaltbare Systeme etabliert ist. Zur Charakterisierung Schichten und zur Untersuchung ihres photoresponsiven Verhaltens sowie sowie zur Untersuchung der Schichtbildung selbst wurden mehrere physikalische Messmethoden angewandt. Die Schichtbildung wurde mit SHG (optische Frequenzverdopplung) verfolgt, die fertigen Schichten wurden mit XPS (Röntgen-Photonen-Spektroskopie) und NEXAFS (Nahkanten-Röntgen-Absorptions-Feinstruktur) untersucht, um Orientierung und Ordnung der Moleküle in der Schicht zu ermitteln. Das Schaltverhalten wurde mit Ellipsometrie und durch Messungen des Wasserkontaktwinkels beobachtet. Durch Variation der Endgruppe des Azobenzols ist es möglich, die Oberflächeneigenschaften einstellen gezielt zu können, wie Hydrophobie, Hydrophilie, Komplexierungsverhalten oder elektrische Schaltbarkeit. Dies gelingt durch Gruppen wie N,N-Dimethylamino-, Methoxy-, Ethoxy-, Octyloxy-, Dodecyloxy-, Benzyloxy-, Methyl-, Trifluormethyl-, Pyridyl-, Phenylethinyl- und Ferrocenyl-Restgruppen, um nur eine Auswahl zu nennen. Einerseits wurde Silizium als Substrat gewählt, da es wegen seiner Verwendung in der Halbleiterindustrie ein nicht uninteressantes Substrat darstell und die Möglichkeiten der kovalenten Anbindung von Trichlorsilanen aber auch Trialkoxysilanen auch gut untersucht ist. Andererseits wurden auch Untersuchungen mit Gold als Substrat angestellt, bei dem Thiole und Disulfide die bevorzugten Ankergruppen bilden. Während sich auf Gold sogenannte SAMs bilden, verleiht die kovalente Siloxanbindung den CAMs auf Silizium eine besondere Stabilität.

Untersuchung der Adsorptionskinetik photoschaltbarer azobenzolfunktionalisierter selbstorganisierter Monolagen mit optischer Frequenzverdopplung

In dieser Arbeit wurde das Adsorptionsverhalten zweier azobenzolfunktionalisierter Liganden auf Goldoberflächen untersucht. Diese Liganden zeichnen sich dadurch aus, dass sie mithilfe von Licht bestimmter Wellenlängen zwischen zwei Isomerisierungszuständen – sowohl in Lösung als auch in den auf der Oberfläche resultierenden Monolage – hin und her geschaltet werden können. Somit ist es möglich, Oberflächen herzustellen, deren physikalische und chemische Eigenschaften zwischen zwei Zuständen variiert werden können. Die Messungen des Adsorptionsverhaltens wurden mittels optischer Frequenzverdopplung durchgeführt. Diese Messmethode ist höchst grenzflächensensitiv und ermöglicht es somit die Adsorption der Liganden in situ und ich Echtzeit zu verfolgen. Neben den Adsorptionsmessungen wurde auch die Phase des frequenzverdoppelten Signals über eine Interferenzmethode gemessen. Die Ergebnisse dieser Phasenmessungen ermöglichen es, eine Aussage über eine mögliche Nichtlinearität der untersuchten Moleküle zu treffen. An die in den Adsorptionsmessungen gewonnenen Messdaten wurden drei kinetische Standardmodelle angepasst. Beschreibt eines dieser Modelle den im Experiment bestimmten Adsorptionsverlauf, kann eine Aussage über die zugrunde liegenden Prozesse des Adsorptionsvorganges getroffen werden. Die Ergebnisse der Adsorptionsmessungen zeigen einen deutlichen Einfluss des Isomerisierungszustandes der Liganden auf den Verlauf der Adsorption. Liegen die Moleküle im geschalteten Zustand vor, so verläuft die Adsorption langsamer. Weiterhin konnte gezeigt werden, dass ebenso intermolekulare Wechselwirkungen über Wasserstoffbrückenbindungen einen verlangsamenden Einfluss auf die Adsorption der Liganden haben. In den durchgeführten Phasenmessungen zeigte sich darüber hinaus, dass Liganden, die über an die Azobenzolgruppe angebundene Amidgruppen verfügen, eine Nichtlinearität aufweisen. Diese Nichtlinearität ist zudem vom Isomerisierungszustand der Liganden abhängig. In den kinetischen Untersuchungen konnte darüber hinaus gezeigt werden, dass sich die Adsorption der Liganden bis auf eine Ausnahme durch die Langmuirkinetik 2. Ordnung beschreiben lässt. Somit handelt es ich bei der Adsorption der untersuchten Liganden um eine Reaktion, der eine Bindungsspaltung voran geht. Dieser Befund konnte durch Vergleich mit weiteren Experimenten bestätigt werden.

A New Class of Nonionic Photosensitive Surfactants: Some Insights Concerning Conformations

We report on a new class of nonionic, photosensitive surfactants consisting of a polar di(ethylene oxide) head group attached to an alkyl spacer of between two and eight methylene groups, coupled through an ether linkage to an azobenzene moiety. Structural changes associated with the interconversion of the azobenzene group between its cis and trans forms as mediated by the wavelength of an irradiating light source cause changes in the surface tension and self-assembly properties. Differences in saturated surface tensions (surface tension at concentrations above the CMC) were as high as 14.4 mN/m under radiation of different wavelengths. The qualitative behavior of the surfactants changed as the spacer length changed, attributed to the different orientations adopted by the different surfactants depending on their isomerization states, as revealed by neutron reflection studies. The self-assembly of these photosensitive surfactants has been investigated by light scattering, small angle neutron scattering, and cryo-TEM under different illuminations. The significant change in the self-assembly in response to different illumination conditions was attributed to the sign change in Gaussian rigidity, which originated from the azobenzene photoisomerization.

Fulvalene cyclopentadienyl titanium and zirconium(III) and -(IV) complexes. X-Ray crystal structure of [{Ti(η5-C5H5) Cl}2 (μ-O)(μ-η5-η5-C10H8)]

The reaction of the fulvalene titanium(III) hydride [{Ti(η5-C5H5)(μ-H)}2(μ-η5-η5-C10H8)] (1) with chlorine leads to [{Ti(η5-C5H5)(μ-Cl)}2(μ-η5-η5-C10H8)] (3) and [{Ti(η5-C5H5)Cl2}2(μ-η5-η5-C10H8)] (4). The reaction of 3 with azobenzene, in wet toluene, gives [{Ti(η5-C5H5)Cl}2(μ-O)(μ-η5-η5-C10H8)] (5) and 1,2-diphenyl hydrazine. The alkylation of 4 and the analogous zirconium complex [{Zr(η5-C5H55)Cl2}2(μ-η5-η5-C10H8)] (2) with LiCH2SiMe3 or LiCH3 permits isolation of the tetraalkyl derivatives [{M(η5-C5H5)(CH2SiMe3)2}2(μ-η5-η5-C10H8)] (M  Ti (6); Zr (8)) and [{Ti(η5-C5H5)(CH3)2}2(μ-η5-η5C10H8)] (7). All the new fulvalene compounds were characterized by IR, and 1H and 13C NMR spectroscope, and mass spectra and 5 by X-ray diffraction. The structure of 5 is very similar to that of the comparable TiIV compound [{Ti(η5-C5H5)2Cl}2(μ-O)] except for the smaller TiOTi angle (159.4° against 173.81°) and a significant deviation from linearity.

Local gratings due to angular hole burning in a photorefractive polymer

We investigate the processes involved in writing real-time holographic gratings in a photorefractive polymer (PRP) that incorporates an azo-dye. In such systems there may be gratings due to mechanisms associated with trans–cis isomerization (angular hole burning (AHB) and/or angular redistribution), which appear in addition to those arising from the photorefractive (PR) effect. The work presented here helps to understand the interactions which may occur between these different gratings. The formation of local gratings due to mechanisms associated with photoisomerization is studied, in a new PRP based on the photoconductor poly(N-vinylcarbazole):2, 4, 7-trinitro-9-fluorenone, plasticized with N-ethylcarbazole. The polymer includes the azo-dye 4-nitro-4'-pentyloxy-azobenzene and we observe both PR and photoisomerization gratings. The gratings are shown to be both polarization-sensitive and reversible. The presence of the photoisomerization gratings (which diffract almost as strongly as the PR gratings) significantly affects the field-dependent diffractive behaviour of the composite. A measurement of the lifetime of the cis state is made (τcis = 38 s) using photoinduced dichroism. This is close to the decay time constant of the local gratings (τdecay = 42 s), and it is suggested that the local grating mechanism is AHB of the azo-dye. This is the first time (to the knowledge of the authors) that a local grating due to AHB has been demonstrated in a PRP.

Azo-group dihedral angle torsion dependence on temperature: A theorerical-experimental study

Quantum chemical calculations were carried out to explain the observed shifts in the absorption spectrum of different azo-aromatic compounds due to changes in the dihedral angle of the azo-group. Our results reveal that the pi-pi* transition presents a hypsochromic shift and an oscillator strength drop upon increase of the dihedral angle. Nevertheless, the pi-pi* transition exhibits the opposite behavior. This effect is attributed to the reduction in the pi-electron conjugation length of the molecule. Experimentally, we performed temperature dependence measurements of the linear absorption spectrum. Both the theoretical and experimental results demonstrate that small energy changes are mirrored in the electronic transitions of conjugated linear molecules. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2`-chloro-4`-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films. (C) 2008 Elsevier Ltd. All rights reserved.

The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

Surface patterns induced by laser irradiation on thin polymer bilayer films

We report on the preparation of wavelike surface patterns with characteristic wavelengths on thin bilayers of poly(methyl methacrylate) on azobenzene liquid crystalline polymer films (LCP/PMMA) by irradiation of a single polarized pulsed laser beam. The formation of such patterns was influenced by the thickness of the upper layer and the laser fluence. We were also able to guide the wavelike pattern to have a specific orientation by placing an elastic polydimethylsiloxane (PDMS) mold on the surface of bilayer film prior to laser irradiation. Moreover, the property of the laser irradiation, that is, the selectivity through mask-projection systems, allowed us fabricating complicated micropattems for novel microdevices. (c) 2007 Elsevier B.V. All rights reserved.

Anisotropic wetting characteristics on submicrometer-scale periodic grooved surface

Submicrometer-scale periodic structures consisting of parallel grooves were prepared on azobenzene-containing multiarm star polymer films by laser interference. The wetting characteristics on the patterned surfaces were studied by contact angle measurements. Macroscopic distortion of water drops was found on such small-scale surface structures, and the contact angles measured from the direction parallel to the grooves were larger than those measured from the perpendicular direction. A thermodynamic model was developed to calculate the change in the surface free energy as a function of the instantaneous contact angle when the three-phase contact line (TPCL) moves along the two orthogonal directions. It was found that the fluctuations, i.e., energy barriers, on the energy versus contact angle curves are crucial to the analysis of wetting anisotropy and contact angle hysteresis. The calculated advancing and receding contact angles from the energy versus contact angle curves were in good agreement with those measured experimentally. Furthermore, with the groove depth increasing, both the degree of wetting anisotropy and the contact angle hysteresis perpendicular to the grooves increased as a result of the increase in the energy barrier. The theoretical critical value of the groove depth, above which the anisotropic wetting appears, was determined to be 16 nm for the grooved surface with a wavelength of 396 nm. On the other hand, the effect of the groove wavelength on the contact angle hysteresis perpendicular to the grooves was also interpreted on the basis of the thermodynamic model. That is, with the wavelength decreasing, the contact angle hysteresis increased due to the increase in the number of energy barriers. These results may provide theoretical evidence for the design and application of anisotropic wetting surface.

Reversible photorheological lyotropic liquid crystals

We describe novel lyotropic liquid-crystalline (LLC) materials based on photoresponsive amphiphiles that exhibit rapid photoswitchable rheological properties of unprecedented magnitude between solidlike and liquidlike states. This was achieved through the synthesis of a novel azobenzene-containing surfactant (azo-surfactant) that actuates the transition between different LLC forms depending on illumination conditions. Initially, the azo-surfactant/water mixtures formed highly ordered and viscous LLC phases at 20-55 wt % water content. Spectroscopic, microscopic, and rheological analysis confirmed that UV irradiation induced the trans to cis isomerization of the azo-surfactant, leading to the disruption of the ordered LLC phases and a dramatic, rapid decrease in the viscosity and modulus resulting in a 3 orders of magnitude change from a solid (20,000 Pa) to a liquid (50 Pa) at rate of 13,500 Pa/s. Subsequent exposure to visible light reverses the transition, returning the viscosity essentially to its initial state. Such large, rapid, and reversible changes in rheological properties within this LLC system may open a door to new applications for photorheological fluids.

Triggering nanoparticle surface ligand rearrangement via external stimuli: light-based actuation of biointerfaces

Bio-molecular non-covalent interactions provide a powerful platform for material-specific self-organization in aqueous media. Here, we introduce a strategy that integrates a synthetic optically-responsive motif with a materials-binding peptide to enable remote actuation. Specifically, we linked a photoswitchable azobenzene moiety to either terminus of a Au-binding peptide. We employed these hybrid molecules as capping agents for synthesis of Au nanoparticles. Integrated experiments and molecular simulations showed that the hybrid molecules maintained both of their functions, i.e. binding to Au and optically-triggered reconfiguration. The azobenzene unit was optically switched reversibly between trans and cis states while adsorbed on the particle surface. Upon switching, the conformation of the peptide component of the molecule also changed. This highlights the interplay between the surface adsorption and conformational switching that will be pivotal to the creation of actuatable nanoparticle bio-interfaces, and paves the way toward multifunctional peptide hybrids that can produce stimuli responsive nanoassemblies.

Photoinduced orientation in natural rubber

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)