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Gegenstand der Arbeit ist die lichtinduzierte Orientierung von multifunktionalen Polymeren, die u.a. für die Herstellung von optischen Schichten in Flüssigkristalldisplays verwendet werden können. Dafür wurden Polymere entwickelt, die wenigstens eine mesogene und eine lichtsensitive Gruppe enthalten. Diese Gruppen zeigen Eigenschaften, die für die Orientierung der kompletten Polymerfilme verantwortlich sind. Das Material wird dafür zunächst in einem ersten Schritt kurz mit linear polarisiertem Licht bestrahlt, wobei richtungsabhängig eine photochemische Reaktion an der lichtsensitiven Gruppe erfolgt und dadurch ein "Orientierungskeim" gelegt wird. Durch die thermische Ausrichtung der mesogenen Gruppen an den photochemisch generierten "Orientierungskeimen" erfolgt die komplette Orientierung des Filmes in einem zweiten Schritt. Dadurch wird eine hohe optische Anisotropie erhalten. Dieses Verfahren wurde als Zwei-Stufen-Bulk-Orientierungsprozess bezeichnet. In der vorliegenden Arbeit wurden die Photoreaktionen verschiedener lichtsensitiver Gruppen, wie z. B. Azobenzen, Stilben und Zimtsäureester und deren Orientierungsfähigkeit in flüssigkristallinen Polymeren untersucht. Der Orientierungsprozess wurde durch die Wahl geeigneter Bestrahlungsbedingungen optimiert. Die Effizienz der Orientierung wurde anhand der sich verändernden winkelabhängigen Absorptionseigenschaften und der Doppelbrechung des Materials analysiert. Es wurde gezeigt, dass eine effiziente lichtinduzierte Orientierung bei einer Vielzahl von flüssigkristallinen Polymeren realisierbar ist. So wurde z. B. erstmalig gefunden, dass durch eine Photo-Fries-Orientierung eine hohe optische Anisotropie erhalten werden kann. Außerdem wurde eine neue lichtsensitive Gruppe auf der Basis von Donor-Akzeptor-substituiertem Ethen entwickelt, die farbneutral ist und durch polarisiertes UV-Licht sowohl orientiert als auch re-orientiert werden kann. Es wurden weiterhin Polymere entwickelt, die zusätzlich zu den photosensitiven und flüssigkristallinen Einheiten, fluoreszierende Gruppen enthalten. Die Auswahl geeigneter Fluoreszenzverbindungen erfolgte aufgrund ihrer anisometrischen Form, ihrer Ordnungsparameter in einer niedermolekularen Flüssigkristallmischung und ihrer Photostabilität. Das Orientierungsverhalten von ausgewählten Fluorophoren wurde in sechs Ter- und zwei Copolymeren untersucht. Das Prinzip der Orientierung beruht auf einer kooperativen Ausrichtung der Seitengruppen. Aus diesem Grund kommt dem Nachweis der Kooperativität in der vorliegenden Arbeit eine besondere Stellung zu. Durch lichtinduzierte Bulk-Orientierung wurden Filme erhalten, welche durch eine richtungsabhängige Fluoreszenz und Absorption im sichtbaren- oder UV-Bereich charakterisiert sind. Die Fluoreszenz wird durch einige lichtsensitive Verbindungen komplett gelöscht. Die wahlweise erhaltenen anisotropen Filme von farbigen, fluoreszierenden oder farbneutralen Verbindungen, die zudem in kleinen Pixeln von wenigen Mikrometern orientiert werden können, eröffnen vielfältige Möglichkeiten für den Einsatz von multi-funktionalen Polymeren als optische Schichten in Flüssigkristalldisplays.
The past two decades witnessed tremendous progress in the field of creation of different types of responsive materials. Cholesteric polymer networks present a very promising class of smart materials due to the combination of the unique optical properties of cholesteric mesophase and high mechanical properties of polymer networks. In the present work we demonstrate the possibility of fast and reversible photocontrol of the optical properties of cholesteric polymer networks. Several cholesteric photopolymerizable mixtures are prepared, and porous cholesteric network films with different helix pitches are produced by polymerization of these mixtures. An effective and simple method of the introduction of photochromic azobenzene-containing nematic mixture capable of isothermal photoinducing the nematic isotropic phase transition into the porous polymer matrix is developed, It is found that cross-linking density and degree of polymer network filling with a photochromic nematic mixture strongly influence the photo-optical behavior of the obtained composite films. In particular, the densely cross-linked films are characterized by a decrease in selective light reflection bandwidth, whereas weakly cross-linked systems display two processes: the shift of selective light reflection peak and decrease of its width. It is noteworthy that the obtained cholesteric materials are shown to be very promising for the variety applications in optoelectronics and photonics.
A new type of self-organized materials based on cholesteric networks filled with photoactive side-chain copolymer is being developed. Supramolecular helical structure of cholesteric polymer network resulting in the selective reflection is used as a photonic scaffold. Photochromic azobenzene-containing nematic copolymer is embedded in cholesteric scaffold and utilized as a photoactive media for optical pattering. 1D and 2D transmission diffraction gratings are successfully recorded in composite films by holographic technique. For the first time the possibility to create selective reflection gratings in cholesteric material mimicking the natural optical properties of cholesteric mesophase is demonstrated. That enables the coexistence of two selective gratings, where one has an intrinsic cholesteric periodic helical structure and the other is a holographic grating generated in photochromic polymer. The full-polymer composites provide high light-induced optical anisotropy due to effective photo-orientation of side-chain fragments of the azobenzene-containing liquid crystalline polymer, and prevent the degradation of the helical superstructure maintaining all optical properties of cholesteric mesophase. The proposed class of optical materials could be easily applied to a broad range of polymeric materials with specific functionality. The versatility of the adjustment and material preprogramming combined with high optical performance makes these materials a highly promising candidate for modern optical and photonic applications.
We review recent progress in the field of light responsive soft nano-objects. These are systems the shape, size, surface area and surface energy of which can be easily changed by low-intensity external irradiation. Here we shall specifically focus on microgels, DNA molecules, polymer brushes and colloidal particles. One convenient way to render these objects photosensitive is to couple them via ionic and/or hydrophobic interactions with azobenzene containing surfactants in a non-covalent way. The advantage of this strategy is that these surfactants can make any type of charged object light responsive without the need for possibly complicated (and irreversible) chemical conjugation. In the following, we will exclusively discuss only photosensitive surfactant systems. These contain a charged head and a hydrophobic tail into which an azobenzene group is incorporated, which can undergo reversible photo-isomerization from a trans-to a cis-configuration under UV illumination. These kinds of photo-isomerizations occur on a picosecond timescale and are fully reversible. The two isomers in general possess different polarity, i.e. the trans-state is less polar with a dipole moment of usually close to 0 Debye, while the cis-isomer has a dipole moment up to 3 Debye or more, depending on additional phenyl ring substituents. As part of the hydrophobic tail of a surfactant molecule, the photo-isomerization also changes the hydrophobicity of the molecule as a whole and hence its solubility, surface energy, and strength of interaction with other substances. Being a molecular actuator, which converts optical energy in to mechanical work, the azobenzene group in the shape of surfactant molecule can be utilized in order to actuate matter on larger time and length scale. In this paper we show several interesting examples, where azobenzene containing surfactants play the role of a transducer mediating between different states of size, shape, surface energy and spatial arrangement of various nanoscale soft-material systems.
This dissertation focuses on the understanding of the optical manipulation of microgels dispersed in aqueous solution of azobenzene containing surfactant. The work consists of three parts where each part is a systematic investigation of the (1) photo-isomerization kinetics of the surfactant in complex with the microgel polymer matrix, (2) light driven diffusiosmosis (LDDO) in microgels and (3) photo-responsivity of microgel on complexation with spiropyran.
The first part comprises three publications where the first one [P1] investigates the photo-isomerization kinetics and corresponding isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged polymers or micro sized polymer networks to understand the structural response of such photo-sensitive complexes. We report that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in an aqueous solution. The surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration. This, along with the inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates, pushes the isomer-ratio to a higher trans-isomer concentration for all irradiation wavelengths.
The second publication [P2] combines experimental results and non-adiabatic dynamic simulations for the same surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the slowdown in photo induced trans → cis azobenzene isomerization at concentrations higher than the critical micelle concentration (CMC). The simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles and observes a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans → cis switching in micelles of the azobenzene-containing surfactants.
Finally, the third publication [P3] focusses on the kinetics of adsorption and desorption of the same surfactant within anionic microgels in the dark and under continuous irradiation. Experimental data demonstrate, that microgels can serve as a selective absorber of the trans isomers. The interaction of the isomers with the gel matrix induces a remotely controllable collapse or swelling on appropriate irradiation wavelengths. Measuring the kinetics of the microgel size response and knowing the exact isomer composition under light exposure, we calculate the adsorption rate of the trans-isomers.
The second part comprises two publications. The first publication [P4] reports on the phenomenon of light-driven diffusioosmotic (DO) long-range attractive and repulsive interactions between micro-sized objects, whose range extends several times the size of microparticles and can be adjusted to point towards or away from the particle by varying irradiation parameters such as intensity or wavelength of light. The phenomenon is fueled by the aforementioned photosensitive surfactant. The complex interaction of dynamic exchange of isomers and photo-isomerization rate yields to relative concentrations gradients of the isomers in the vicinity of micro-sized object inducing a local diffusioosmotic (DO) flow thereby making a surface act as a micropump.
The second publication [P5] exclusively aims the visualization and investigation of the DO flows generated from microgels by using small tracer particles. Similar to micro sized objects, the flow is able to push adjacent tracers over distances several times larger than microgel size. Here we report that the direction and the strength of the l-LDDO depends on the intensity, irradiation wavelength and the amount of surfactant adsorbed by the microgel. For example, the flow pattern around a microgel is directed radially outward and can be maintained quasi-indefinitely under exposure at 455 nm when the trans:cis ratio is 2:1, whereas irradiation at 365 nm, generates a radially transient flow pattern, which inverts at lower intensities.
Lastly, the third part consists of one publication [P6] which, unlike the previous works, reports on the study of the kinetics of photo- and thermo-switching of a new surfactant namely, spiropyran, upon exposure with light of different wavelengths and its interaction with p(NIPAM-AA) microgels. The surfactant being an amphiphile, switches between its ring closed spiropyran (SP) form and ring open merocyanine (MC) form which results in a change in the hydrophilic–hydrophobic balance of the surfactant as MC being a zwitterionic form along with the charged head group, generates three charges on the molecule. Therefore, the MC form of the surfactant is more hydrophilic than in the case of the neutral SP state. Here, we investigate the initial shrinkage of the gel particles via charge compensation on first exposure to SP molecules which results from the complex formation of the molecules with the gel matrix, triggering them to become photo responsive. The size and VPTT of the microgels during irradiation is shown to be a combination of heating up of the solution during light absorption by the surfactant (more pronounced in the case of UV irradiation) and the change in the hydrophobicity of the surfactant.
Photo-Isomerization Kinetics of Azobenzene Containing Surfactant Conjugated with Polyelectrolyte
(2020)
Ionic complexation of azobenzene-containing surfactants with any type of oppositely charged soft objects allows for making them photo-responsive in terms of their size, shape and surface energy. Investigation of the photo-isomerization kinetic and isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged objects is a necessary prerequisite for understanding the structural response of photo-sensitive complexes. Here, we report on photo-isomerization kinetics of a photo-sensitive surfactant in the presence of poly(acrylic acid, sodium salt). We show that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in aqueous solution. In a photo-stationary state, the ratio between the trans and cis isomers is shifted to a higher trans-isomer concentration for all irradiation wavelengths. This is explained by the formation of surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration and inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates.
Photo-Isomerization Kinetics of Azobenzene Containing Surfactant Conjugated with Polyelectrolyte
(2020)
Ionic complexation of azobenzene-containing surfactants with any type of oppositely charged soft objects allows for making them photo-responsive in terms of their size, shape and surface energy. Investigation of the photo-isomerization kinetic and isomer composition at a photo-stationary state of the photo-sensitive surfactant conjugated with charged objects is a necessary prerequisite for understanding the structural response of photo-sensitive complexes. Here, we report on photo-isomerization kinetics of a photo-sensitive surfactant in the presence of poly(acrylic acid, sodium salt). We show that the photo-isomerization of the azobenzene-containing cationic surfactant is slower in a polymer complex compared to being purely dissolved in aqueous solution. In a photo-stationary state, the ratio between the trans and cis isomers is shifted to a higher trans-isomer concentration for all irradiation wavelengths. This is explained by the formation of surfactant aggregates near the polyelectrolyte chains at concentrations much lower than the bulk critical micelle concentration and inhibition of the photo-isomerization kinetics due to steric hindrance within the densely packed aggregates.
Azobenzene-containing molecules may associate with each other in systems such as self-assembled monolayers or micelles. The interaction between azobenzene units leads to a formation of exciton states in these molecular assemblies. Apart from local excitations of monomers, the electronic transitions to the exciton states may involve charge transfer excitations. Here, we perform quantum chemical calculations and apply transition density matrix analysis to quantify local and charge transfer contributions to the lowest electronic transitions in azobenzene dimers of various arrangements. We find that the transitions to the lowest exciton states of the considered dimers are dominated by local excitations, but charge transfer contributions become sizable for some of the lowest pi pi* electronic transitions in stacked and slip-stacked dimers at short intermolecular distances. In addition, we assess different ways to partition the transition density matrix between fragments. In particular, we find that the inclusion of the atomic orbital overlap has a pronounced effect on quantifying charge transfer contributions if a large basis set is used.
This cumulative doctoral dissertation, based on three publications, is devoted to the investigation of several aspects of azobenzene molecular switches, with the aid of computational chemistry.
In the first paper, the isomerization rates of a thermal cis → trans isomerization of azobenzenes for species formed upon an integer electron transfer, i.e., with added or removed electron, are calculated from Eyring’s transition state theory and activation energy barriers, computed by means of density functional theory. The obtained results are discussed in connection with an experimental study of the thermal cis → trans isomerization of azobenzene derivatives in the presence of gold nanoparticles, which is demonstrated to be greatly accelerated in comparison to the same isomerization reaction in the absence of nanoparticles.
The second paper is concerned with electronically excited states of (i) dimers, composed of two photoswitchable units placed closely side-by-side, as well as (ii) monomers and dimers adsorbed on a silicon cluster. A variety of quantum chemistry methods, capable of calculating molecular electronic absorption spectra, based on density functional and wave function theories, is employed to quantify changes in optical absorption upon dimerization and covalent grafting to a surface. Specifically, the exciton (Davydov) splitting between states of interest is determined from first-principles calculations with the help of natural transition orbital analysis, allowing for insight into the nature of excited states.
In the third paper, nonadiabatic molecular dynamics with trajectory surface hopping is applied to model the photoisomerization of azobenzene dimers, (i) for the isolated case (exhibiting the exciton coupling between two molecules) as well as (ii) for the constrained case (providing the van der Waals interaction with environment in addition to the exciton coupling between two monomers). For the latter, the additional azobenzene molecules, surrounding the dimer, are introduced, mimicking a densely packed self-assembled monolayer. From obtained results it is concluded that the isolated dimer is capable of isomerization likewise the monomer, whereas the steric hindrance considerably suppresses trans → cis photoisomerization.
Furthermore, the present dissertation comprises the general introduction describing the main features of the azobenzene photoswitch and objectives of this work, theoretical basis of the employed methods, and discussion of gained findings in the light of existing literature. Also, additional results on (i) activation parameters of the thermal cis → trans isomerization of azobenzenes, (ii) an approximate scheme to account for anharmonicity of molecular vibrations in calculation of the activation entropy, as well as (iii) absorption spectra of photoswitch–silicon composites obtained from time-demanding wave function-based methods are presented.
Photosensitive azobenzene-containing surfactants have attracted great attention in past years because they offer a means to control soft-matter transformations with light. At concentrations higher than the critical micelle concentration (CMC), the surfactant molecules aggregate and form micelles, which leads to a slowdown of the photoinduced trans -> cis azobenzene isomerization. Here, we combine nonadiabatic dynamics simulations for the surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the reaction slowdown. Our simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles. We also observe a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans -> cis switching in micelles of the azobenzene-containing surfactants.