Arri Priimagi

Azobenzene photomechanics: prospects and potential applications

The change in shape inducible in some photo-reversible molecules using light can effect powerful changes to a variety of properties of a host material. This class of reversible light-switchable molecules includes molecules that photo-dimerize, such as coumarins and anthracenes; those that allow intra-molecular photo-induced bond formation, such as fulgides, spiro-pyrans, and diarylethenes; and those that exhibit photo-isomerization, such as stilbenes, crowded alkenes, and azobenzenes. The most ubiquitous natural molecule for reversible shape change, however, and perhaps the inspiration for all artificial bio-mimics, is the rhodopsin/retinal protein system that enables vision, and this is the quintessential reversible photo-switch for performance and robustness. Here, the small retinal molecule embedded in a cage of rhodopsin helices isomerizes from a cis geometry to a trans geometry around a C=C double bond with the absorption of just a single photon. The modest shape change of just a few angstroms is quickly amplified and sets off a cascade of larger shape and chemical changes, eventually culminating in an electrical signal to the brain of a vision event, the energy of the input photon amplified many thousands of times in the process. Complicated biochemical pathways then revert the trans isomer back to cis, and set the system back up for another cascade upon subsequent absorption. The reversibility is complete, and many subsequent cycles are possible. The reversion mechanism back to the initial cis state is complex and enzymatic, hence direct application of the retinal/rhodopsin photo-switch to engineering systems is difficult. Perhaps the best artificial mimic of this strong photo-switching effect however in terms of reversibility, speed, and simplicity of incorporation, is azobenzene. Trans and cis states can be switched in microseconds with low-power light, reversibility of 105 and 106 cycles is routine before chemical fatigue, and a wide variety of molecular architectures is available to the synthetic materials chemist, permitting facile anchoring and compatibility, as well as chemical and physical amplification of the simple geometric change. This review article focuses on photo-mechanical effect taking place in various material systems incorporating azobenzene. The photo-mechanical effect can be defined as reversible change in shape by absorption of light, which results in a significant macroscopic mechanical deformation, and reversible mechanical actuation, of the host material. Thus, we exclude simple thermal expansion effects, reversible but non-mechanical photo-switching or photo-chemistry, as well as the wide range of optical and electro-optical switching effects for which good reviews exist elsewhere. Azobenzene-based material systems are also of great interest for light energy harvesting applications across much of the solar spectrum, yet this emerging field is still in an early enough stage of research output as to not yet warrant review, but we hope that some of the ideas put forward here toward promising future directions of research, will help guide the field.

Recent twists in photoactuation and photoalignment control

The design of functional and stimuli-responsive materials is among the key goals of modern materials science. The structure and properties of such materials can be controlled via various stimuli, among which light is often times the most attractive choice. Light is ubiquitous and a gentle energy source and its properties can be optimized for a specific target remotely, with high spatial and temporal resolution. Light-control over molecular alignment has in recent years attracted particular interest, for potential applications such as reconfigurable photonic elements and optical-to-mechanical energy conversion. Herein, we bring forward some recent examples and emerging trends in this exciting field of research, focusing on liquid crystals, liquid-crystalline polymers and photochromic organic crystals, which we believe serve to highlight the immense potential of light-responsive materials to a wide variety of current and future high-tech applications in photonics, energy harvesting and conversion.

Optical Interference Lithography Using Azobenzene‐Functionalized Polymers for Micro‐ and Nanopatterning of Silicon

Azobenzene-containing polymers (azopolymers) have attracted great interest due to their potential use in various technological applications, including holographic recording, photomechanics, diffractive optics, and microand nanopatterning. [ 1–7 ] These applications are brought about by the effi cient and reversible photoisomerization of the azobenzene moieties between a rodlike trans-state and a bent cis-state, which is accompanied by various changes in the properties of the material system both at molecular and macroscopic levels. [ 7 , 8 ] Remarkably, the photoisomerization can give rise to signifi cant surface mass transport phenomena, allowing one-step inscription of high-quality, thermally stable photoinduced surface patterns onto the azopolymer fi lm. Since its fi rst demonstration in 1995, [ 9 , 10 ] the photoinduced surface-relief grating (SRG) formation has been intensively investigated in various types of azobenzene-containing materials. [ 11–15 ] The phenomenon continually keeps fi nding new potential applications. Recently, the SRGs have been combined with organic solar cells and lasers, [ 16 , 17 ] carbon-based nanomaterials, [ 18 ] and block-copolymer nanostructures. [ 19 ] Furthermore, in recent years, azopolymer-based patterns have been increasingly used as templates for fabricating periodic arrays of, e.g., titanium dioxide, [ 20–22 ] indium tin oxide, [ 23 ] and metallic [ 24 , 25 ]

Redox‐Active, Organometallic Surface‐Relief Gratings from Azobenzene‐Containing Polyferrocenylsilane Block Copolymers

Organometallic gratings: the ionic self-assembly of metal-containing block-copolymer polyelectrolytes and azobenzene chromophores is exploited for the efficient production of stable photo-induced surface-relief gratings. We show that feature sizes can be tuned using simple redox chemistry, and that the chromophores can be removed during plasma treatment to yield ceramic-based optical materials.

Supramolecular hierarchy among halogen and hydrogen bond donors in light-induced surface patterning†

Halogen bonding, a noncovalent interaction possessing several unique features compared to the more familiar hydrogen bonding, is emerging as a powerful tool in functional materials design. Herein, we unambiguously show that one of these characteristic features, namely high directionality, renders halogen bonding the interaction of choice when developing azobenzene-containing supramolecular polymers for light-induced surface patterning. The study is conducted by using an extensive library of azobenzene molecules that differ only in terms of the bond-donor unit. We introduce a new tetrafluorophenol-containing azobenzene photoswitch capable of forming strong hydrogen bonds, and show that an iodoethynyl-containing azobenzene comes out on top of the supramolecular hierarchy to provide unprecedented photoinduced surface patterning efficiency. Specifically, the iodoethynyl motif seems highly promising in future development of polymeric optical and photoactive materials driven by halogen bonding.

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.

Efficient surface structuring and photoalignment of supramolecular polymer–azobenzene complexes through rational chromophore design

Rational selection of the para-substituent of azobenzene chromophores in supramolecular polymeric complexes is exploited to control the chromophore–chromophore intermolecular interactions occurring in the material system. This allows optimizing the material system for either efficient surface-relief formation or for high and stable photoalignment. The surface-relief gratings can be subsequently coated with amorphous TiO2 using atomic layer deposition, resulting in high-quality and high-index organic–inorganic gratings with vastly improved thermal stability compared to all-polymeric gratings.

Halogen bonding enhances nonlinear optical response in poled supramolecular polymers

We demonstrate that halogen bonding strongly enhances the nonlinear optical response of poled supramolecular polymer systems. We compare three nonlinear optical chromophores with similar electronic structures but different bond-donating units, and show that both the type and the strength of the noncovalent interaction between the chromophores and the polymer matrix play their own distinctive roles in the optical nonlinearity of the systems.

Photoalignment and Surface‐Relief‐Grating Formation are Efficiently Combined in Low‐Molecular‐Weight Halogen‐Bonded Complexes

It is demonstrated that halogen bonding can be used to construct low-molecular-weight supramolecular complexes with unique light-responsive properties. In particular, halogen bonding drives the formation of a photoresponsive liquid-crystalline complex between a non-mesogenic halogen bond-donor molecule incorporating an azo group, and a non-mesogenic alkoxystilbazole moiety, acting as a halogen bond-acceptor. Upon irradiation with polarized light, the complex exhibits a high degree of photoinduced anisotropy (order parameter of molecular alignment > 0.5). Moreover, efficient photoinduced surface-relief-grating (SRG) formation occurs upon irradiation with a light interference pattern, with a surface-modulation depth 2.4 times the initial film thickness. This is the first report on a halogen-bonded photoresponsive low-molecular-weight complex, which furthermore combines a high degree of photoalignment and extremely efficient SRG formation in a unique way. This study highlights the potential of halogen bonding as a new tool for the rational design of high-performance photoresponsive suprastructures.

Facile strain analysis of largely bending films by a surface-labelled grating method

Mechanical properties of flexible films, for example surface strain of largely bending films, are key to design of stretchable electronic devices, wearable biointegrated devices, and soft microactuators/robots. However, existing methods are mainly based on strain-gauge measurements that require miniaturized array sensors, lead wires, and complicated calibrations. Here we introduce a facile method, based on surface-labelled gratings, for two-dimensional evaluation of surface strains in largely bending films. With this technique, we demonstrate that soft-matter mechanics can be distinct from the mechanics of hard materials. In particular, liquid-crystalline elastomers may undergo unconventional bending in three dimensions, in which both the inner and outer surfaces of the bending film are compressed. We also show that this method can be applied to amorphous elastomeric films, which highlights the general importance of this new mechanical evaluation tool in designing soft-matter-based electronic/photonic as well as biointegrated materials.