New tricks and emerging applications from contemporary azobenzene research.

Azobenzenes have many faces. They are well-known as dyes, but most of all, azobenzenes are versatile photoswitchable molecules with powerful photochemical properties. Azobenzene photochemistry has been extensively studied for decades, but only relatively recently research has taken a steer towards applications, ranging from photonics and robotics to photobiology. In this perspective, after an overview of the recent trends in the molecular design of azobenzenes, we highlight three research areas where the azobenzene photoswitches may bring about promising technological innovations: chemical sensing, organic transistors, and cell signaling. Ingenious molecular designs have enabled versatile control of azobenzene photochemical properties, which has in turn facilitated the development of chemical sensors and photoswitchable organic transistors. Finally, the power of azobenzenes in biology is exemplified by vision restoration and photactivation of neural signaling. Although the selected examples reveal only some of the faces of azobenzenes, we expect the fields presented to develop rapidly in the near future, and that azobenzenes will play a central role in this development.

On the molecular optical nonlinearity of halogen-bond-forming azobenzenes.

We study hyper-Rayleigh scattering and computed molecular hyperpolarizability in a series of azobenzene chromophores in chloroform and dimethylformamide as solvents. The chromophores form halogen or hydrogen bonds of varying strength with dimethylformamide molecules, differently from what is expected for chloroform. We show that hyperpolarizability is unaffected or sligthly lower with the azobenzene forming the strongest halogen bond. Solid supramolecular polymers with the same chromophores have previously demonstrated clearly higher second-order nonlinear responses when a halogen-bond-accepting polymer is used, the larger increase being associated with the stronger halogen bond. The present study proves that the higher optical nonlinearity in polymers lies in the better ordering of the chromophores instead of changes in molecular hyperpolarizability, highlighting the unique properties of halogen bonding in supramolecular chemistry.

Photoresponsive ionic liquid crystals assembled via halogen bond: en route towards light-controllable ion transporters.

We demonstrate that halogen bonding (XB) can offer a novel approach for the construction of photoresponsive ionic liquid crystals. In particular, we assembled two new supramolecular complexes based on 1-ethyl-3-methylimidazolium iodides and azobenzene derivatives containing an iodotetrafluoro-benzene ring as XB donor, where the iodide anion acted as an XB acceptor. DSC and X-ray diffraction analyses revealed that the preferred stoichiometry between the XB donors and acceptors is 2 : 1, and that the iodide anions act as bidentate XB-acceptors, binding two azobenzene derivatives. Due to the high directionality of the XB, calamitic superanions are obtained, while the segregation occurring between the charged and uncharged parts of the molecules gives rise to a layered structure in the crystal lattice. Despite the fact that the starting materials are non-mesomorphic, the halogen-bonded supramolecular complexes exhibited monotropic lamellar liquid-crystalline phases over broad temperature ranges, as confirmed with polarized optical microscopy. Due to the presence of the azobenzene moieties, the LCs were photoresponsive, and a LC-to-isotropic phase transition could be obtained by irradiation with UV light. We envisage that the light-induced phase transition, in combination with the ionic nature of the LC, provides a route towards light-induced control over ion transport and conductance in these supramolecular complexes.

Surface-Relief Gratings in Halogen-Bonded Polymer-Azobenzene Complexes: A Concentration-Dependence Study.

In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer-azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer-azobenzene complexes.

Photoinduced nonlinear optical response in azobenzene-functionalized molecular glass.

We show that mexylaminotriazine molecular glass functionalized with the azobenzene derivative Disperse Red 1 shows equally strong second-order nonlinear optical response as well-known polymers with the same photoactive component. Furthermore, even high chromophore loading does not adversely affect the nonlinear response. This suggests that chromophore-chromophore intermolecular interactions do not greatly limit the response of such molecular glasses, which therefore provide an excellent materials platform for nonlinear optical applications.

Red-light photoswitching of indigos in polymer thin films.

Through simple synthetic derivatisation, the parent indigo dye becomes a red-light E-Z photoswitch exhibiting negative photochromism and tuneable thermal isomerisation kinetics. These attributes make indigo derivatives extremely attractive for applications related to materials and living systems. However, there is a lack of knowledge in translating indigo photoswitching dynamics from solution to solid state - the environment crucial for most applications. Herein, we study the photoswitching performance of six structurally distinct indigo derivatives in five polymers of varying rigidity. Three key strategies are identified to enable efficient photoswitching under red (660 nm) light: (i) choosing a soft polymer matrix to minimise its resistance toward the isomerisation, (ii) creating free volume around the indigo molecules through synthetic modifications, and (iii) applying low dye loading (<1% w/w) to inhibit aggregation. These strategies are shown to improve both photostationary state distributions and the thermal stability of the Z isomer. When all three strategies are implemented, the isomerisation performance (>80% Z form in the photostationary state) is nearly identical to that in solution. These findings thus pave the way for designing new red-light photochromic materials based on indigos.

Expanding excitation wavelengths for azobenzene photoswitching into the near-infrared range via endothermic triplet energy transfer.

Developing azobenzene photoswitches capable of selective and efficient photoisomerization by long-wavelength excitation is an enduring challenge. Herein, rapid isomerization from the Z- to E-state of two ortho-functionalized bistable azobenzenes with near-unity photoconversion efficiency was driven by triplet energy transfer upon red and near-infrared (up to 770 nm) excitation of porphyrin photosensitizers in catalytic micromolar concentrations. We show that the process of triplet-sensitized isomerization is efficient even when the sensitizer triplet energy is substantially lower (>200 meV) than that of the azobenzene used. This makes the approach applicable for a wide variety of sensitizer-azobenzene combinations and enables the expansion of excitation wavelengths into the near-infrared spectral range. Therefore, indirect excitation via endothermic triplet energy transfer provides efficient and precise means for photoswitching upon 770 nm near-infared light illumination with no chemical modification of the azobenzene chromophore, a desirable feature in photocontrollable biomaterials.

Digital holographic microscopy for real-time observation of surface-relief grating formation on azobenzene-containing films.

Light-induced surface structuring of azobenzene-containing films allows for creation of complex surface relief patterns with varying heights, patterns which would be difficult to create using conventional lithography tools. In order to realize the full potential of these patternable surfaces, understanding their formation dynamics and response to different types of light fields is crucial. In the present work we introduce digital holographic microscopy (DHM) for real time, in-situ observation of surface-relief grating (SRG) formation on azobenzene-containing films. This instrument allows us to measure the surface topography of films while illuminating them with two individually controlled laser beams for creating periodically varying patterns. By utilizing the information of the grating formation dynamics, we combine multiple grating patterns to create pixels with wide gamut structural colors as well as blazed grating structures on the film surface. As long as the material behaviour is linear, any Fourier optical surface can be created utilizing this multiple patterning approach. The DHM instrument presented here has the potential for creating complex 3D surface reliefs with nanometric precision.

Surface-Enhanced Impulsive Coherent Vibrational Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) has attracted a lot of attention in molecular sensing because of the remarkable ability of plasmonic metal nanostructures to enhance the weak Raman scattering process. On the other hand, coherent vibrational spectroscopy triggered by impulsive excitation using ultrafast laser pulses provides complete information about the temporal evolution of molecular vibrations, allowing dynamical processes in molecular systems to be followed in "real time". Here, we combine these two concepts and demonstrate surface-enhanced impulsive vibrational spectroscopy. The vibrational modes of the ground and excited states of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), spin-coated on a substrate covered with monodisperse silver nanoparticles, are impulsively excited with a sub-10 fs pump pulse and characterized with a delayed broad-band probe pulse. The maximum enhancement in the spectrally and temporally resolved vibrational signatures averaged over the whole sample is about 4.6, while the real-time information about the instantaneous vibrational amplitude together with the initial vibrational phase is preserved. The phase is essential to determine the vibrational contributions from the ground and excited states.

High-contrast photoswitching of nonlinear optical response in crosslinked ferroelectric liquid-crystalline polymers.

A conceptually novel materials design, based on crosslinked ferroelectric liquid-crystalline polymers, is demonstrated for efficient switching of a second-order nonlinear optical (NLO) response in the solid state. By controlling the molecular alignment of the NLO moieties through two-photon isomerization of azobenzene molecules, reversible isothermal photocontrol of second-harmonic generation is achieved with contrast of up to 20.

Size-controlled aerosol synthesis of silver nanoparticles for plasmonic materials.

Aerosol techniques were used to synthesize spherical and monodisperse silver nanoparticles for plasmonic materials. The particles were generated with an evaporation-condensation technique followed by size selection and sintering with a differential mobility analyzer and a tube furnace, respectively. Finally, the nanoparticles were collected on a glass substrate with an electrostatic precipitator. The particle size distributions were measured with a scanning mobility particle sizer and verified with a transmission electron microscope. A spectrophotometer was used to measure the optical extinction spectra of the prepared samples, which contained particles with diameters of approximately 50, 90 and 130 nm. By controlling the particle size, the dipolar peak of the localized surface plasmon resonance was tuned between wavelengths of 398 and 448 nm. In addition, quadrupolar resonances were observed at shorter wavelengths as predicted by the simplified theoretical model used to characterize the measured spectra.