Picosecond Switchable Azo Dyes.

Azo dyes that combine electron-withdrawing thiazole/benzothiazole heterocycles and electron-donating amino groups within the very same covalent skeleton exhibit relaxation times for their thermal isomerization kinetics within milli- and microsecond timescales at room temperature. Notably, the thermal back reaction of the corresponding benzothiazolium and thiazolium salts occurred much faster, within the picosecond temporal domain. In fact, these new light-sensitive platforms are the first molecular azo derivatives capable of reversible switching between their trans and cis isomers in a subnanosecond timescale under ambient conditions. In addition, theoretical calculations revealed very low activation energies for the isomerization process, in accordance with the fast subnanosecond kinetics that were observed experimentally.

Formation of a stable biradical triplet state cation versus a closed shell singlet state cation by oxidation of adducts of 3,6-dimethoxycarbazole and polychlorotriphenylmethyl radicals.

We report an experimental and theoretical study of two stable radical adducts of the triphenylmethyl series, 1 and 2, whose composition and molecular structure are distinguished by the content and position of chlorine atoms in phenyls. The electrochemical study through cyclic voltammetry of these open layer species shows the existence of two reversible processes, related to reduction and oxidation, to stable charged species. The chemical oxidation of both radical adducts gives rise to stable cations, whose fundamental state has a biradical triplet electronic structure or a closed shell singlet character, depending on the electronic conjugation between the donor and acceptor electron moieties. The presence of chlorines adjacent to the nitrogen in 1 breaks the conjugation between both halves, facilitating the formation of a triplet electronic state of the cation, while the absence of chlorines in these positions in 2 facilitates partial conjugation and stabilizes the closed shell singlet electronic state of the cation.

Solid-state organization of n-type carbazole-based semiconductors for organic thin-film transistors.

The development of new organic semiconductors has been mainly led by the search for new π-conjugated cores, but recently the use of flexible side chains is attracting more and more attention to control the molecular packing and order in the solid state to improve the charge-transporting properties. In this work, the charge transport properties of a series of tricyanovinyl-substituted carbazole-based materials with different alkyl chain lengths have been investigated and correlated with the respective intermolecular interactions and molecular packings via X-ray diffraction (XRD) studies.

Interface engineering and solid-state organization for triindole-based p-type organic thin-film transistors.

Inspired by the excellent device performance of triindole-based semiconductors in electronic and optoelectronic devices, the relationship between the solid-state organization and the charge-transporting properties of an easily accessible series of triindole derivatives is reported herein. The vacuum-evaporated organic thin-film transistors (OTFTs) exhibited a non ideal behaviour with a double slope in the saturation curves. Moreover, the treatment of the gate insulator of the OTFT device with either a self-assembled monolayer (SAM) or a polymer controls the molecular growth and the film morphology of the semiconducting layer, as shown by X-ray diffraction (XRD) analyses, atomic force microscopy (AFM) and theoretical calculations. N-Trihexyltriindole exhibited the best device performance with hole mobilities up to 0.1 cm2 V-1 s-1 at the low VG range and up to 0.01 cm2 V-1 s-1 at high VG, as well as enhanced Ion/Ioff ratios of around 106. The results suggest that the non-ideal behaviour of the here studied OTFT devices could be related to the higher interfacial disorder in comparison to that in the bulk.

Activation volumes for cis-to-trans isomerisation reactions of azophenols: a clear mechanistic indicator?

The thermal cis-to-trans isomerisation reaction of a series of hydroxy-substituted azo derivatives was studied kinetico-mechanistically as a function of temperature and pressure in order to investigate the possible role of the solvent in controlling the isomerisation mechanism, viz. inversion versus rotation. The variation of the observed first order rate constants for kinetic runs carried out at different temperatures and pressures was used to determine the thermal activation parameters ΔH‡ and ΔS‡, and the pressure activation parameter ΔV‡. In addition, some experiments with deuterated species or solvents were also performed. The reported results could be interpreted as indicative of a changeover from an inversion mechanism for non-polar solvents to a rotational mechanism for polar solvents, capable of hydrogen bonding, for some of the systems studied. However, the operation of a rotational mechanism in all studied cases can account more consistently for the data observed.

Development of Green/Red-Absorbing Chromophores Based on a Coumarin Scaffold That Are Useful as Caging Groups.

We report the design, synthesis, and spectroscopic characterization of a series of push-pull chromophores based on a novel coumarin scaffold in which the carbonyl of the lactone function of the original coumarin dyes has been replaced by the cyano(4-nitrophenyl)methylene moiety. The skeleton of the compounds was synthesized by condensation of a thiocoumarin precursor with the corresponding arylacetonitrile derivatives, and their photophysical properties were fine-tuned through the incorporation of electron-withdrawing groups (EWGs) like nitro and cyano at the phenyl ring, leading to absorption in the green to red region. Although fluorescence emission was weakened or even canceled upon introduction of two or three strong EWGs, the emission of the mononitro-containing coumarin derivatives in the red region upon excitation with green light is noticeable, as are their significantly large Stokes shifts. The new coumarin derivatives can be useful as photocleavable protecting groups, as demonstrated through the synthesis and characterization of a series of coumarin-based photocages of benzoic acid. Preliminary photolysis studies with green light have demonstrated that the structure of the coumarin chromophore influences the rate of the uncaging process, opening the way to exploiting these new coumarin scaffolds as caging groups that can be removed with visible light.

Tuning the ambipolar charge transport properties of tricyanovinyl-substituted carbazole-based materials.

A series of push-pull carbazole-based compounds has been experimentally and theoretically characterized in combination with the X-ray analysis of the corresponding single crystals. The introduction of the strong electron-withdrawing tricyanovinyl group in the carbazole core affords electron-transporting ability in addition to the characteristic hole-transporting properties exhibited by donor carbazole derivatives.

Stable All-Organic Radicals with Ambipolar Charge Transport.

A series of neutral long-lived purely organic radicals based on the stable [4-(N-carbazolyl)-2,6-dichlorophenyl]bis(2,4,6-trichlorophenyl)methyl radical adduct (Cbz-TTM) is reported herein. All compounds exhibit ambipolar charge-transport properties under ambient conditions owing to their radical character. High electron and hole mobilities up to 10-2 and 10-3  cm2 V-1 s-1 , respectively, were achieved. Xerographic single-layered photoreceptors were fabricated from the radicals studied herein, exhibiting good xerographic photosensitivity across the visible spectrum.

Exploring optical mechanotransduction in fluorescent liquid crystal elastomers.

Carbazole-based nematic liquid single crystal elastomers switch their fluorescence mechanically on demand enabling a fast optical mechanotransduction under ambient conditions. The identification of the key factors controlling such process is of utmost importance since it might lead to a significant improvement of the transducing abilities of these smart materials. In particular, variations in the length of the fluorophore flexible spacer translates in a distinct mutual interaction between both mesogenic and fluorogenic platforms, giving rise thereby to functional materials with a significantly different mechanofluorescent behaviour.

Spatially close azo dyes with sub-nanosecond switching speeds and exceptional temporal resolution.

Photoswitchable bis-azo dyes with an outstanding temporal resolution of 10(15) times between the thermal relaxation rates of their two constituting photochromes are reported. Remarkably, the close spatial proximity of both azo photochromes in these molecular assemblies translates in an unprecedented 10(3) -fold acceleration of the thermal isomerization rate of their faster azo unit compared to the one displayed by the isolated counterpart. Indeed, the relaxation time of the fast-isomerizing platform of the herein reported bis-azobenzenes is as low as 200 ps under ambient conditions. In the wake of these results, the bis-azo dyes described herein are invaluable chromophores for the design of multifunctional light-addressable materials in which simultaneous switching in two very different timescales might be essential.

Correction: Selective photoregulation of the activity of glycogen synthase and glycogen phosphorylase, two key enzymes in glycogen metabolism.

Correction for 'Selective photoregulation of the activity of glycogen synthase and glycogen phosphorylase, two key enzymes in glycogen metabolism' by Mireia Díaz-Lobo, et al., Org. Biomol. Chem., 2015, 13, 7282-7288.

Selective photoregulation of the activity of glycogen synthase and glycogen phosphorylase, two key enzymes in glycogen metabolism.

Glycogen is a polymer of α-1,4- and α-1,6-linked glucose units that provides a readily available source of energy in living organisms. Glycogen synthase (GS) and glycogen phosphorylase (GP) are the two enzymes that control, respectively, the synthesis and degradation of this polysaccharide and constitute adequate pharmacological targets to modulate cellular glycogen levels, by means of inhibition of their catalytic activity. Here we report on the synthesis and biological evaluation of a selective inhibitor that consists of an azobenzene moiety glycosidically linked to the anomeric carbon of a glucose molecule. In the ground state, the more stable (E)-isomer of the azobenzene glucoside had a slight inhibitory effect on rat muscle GP (RMGP, IC50 = 4.9 mM) and Escherichia coli GS (EcGS, IC50 = 1.6 mM). After irradiation and subsequent conversion to the (Z)-form, the inhibitory potency of the azobenzene glucoside did not significantly change for RMGP (IC50 = 2.4 mM), while its effect on EcGS increased 50-fold (IC50 = 32 µM). Sucrose synthase 4 from potatoes, a glycosyltransferase that does not operate on glycogen, was only slightly inhibited by the (E)-isomer (IC50 = 0.73 mM). These findings could be rationalized on the basis of kinetic and computer-aided docking analysis, which indicated that both isomers of the azobenzene glucoside mimic the EcGS acceptor substrate and exert their inhibitory effect by binding to the glycogen subsite in the active center of the enzyme. The ability to selectively photoregulate the catalytic activity of key enzymes of glycogen metabolism may represent a new approach for the treatment of glycogen metabolism disorders.

Optical mechanotransduction with carbazole-based luminescent liquid single-crystal elastomers.

Carbazole-based liquid single-crystal elastomers (LSCEs) are valuable fluorescent flexible materials to perform optical mechanotransduction under ambient conditions. Indeed, the covalent incorporation of carbazole derivatives into nematic LSCEs allows to tune their luminescence on demand under mechanical control in a quick and reversible fashion. Specifically, the fluorescence intensity for these materials can be switched back and forth in less than a second. Moreover, such a process can be performed several times without detecting any sign of fatigue in the system. In addition, these materials show excellent resistance to aging; 2 years after their preparation they exhibit the very same mechanofluorescent behavior as when freshly prepared. In fact, the here reported fluorescent systems are highly sensitive; the application of a force of 70 mN decreases the fluorescence in the elastomeric material by 7%. Thus, mechanical forces are attractive external stimuli to modulate the fluorescence of nematic elastomers rapidly and reversibly enabling thereby mechanotransduction.

Charge transfer states in stable neutral and oxidized radical adducts from carbazole derivatives.

In this paper we report the spectral properties of the stable radical adducts 1(•)-3(•), which are formed by an electron donor moiety, the carbazole ring, and an electron acceptor moiety, the polychlorotriphenylmethyl radical. The molecular structure of radical adduct 1(•) in the crystalline state shows a torsion angle of approximately 90° between the phenyl and the carbazole rings due to steric interactions. They exhibit a charge transfer band in the visible range of the electronic spectrum. All of them are chemically oxidized with copper(II) perchlorate to the respective cation species, which show a strong charge transfer band into the near-infrared region of the spectrum. Radical adducts 1(•)-3(•) and the corresponding stable oxidized species 1(+)-3(+) are real organic mixed-valence compounds due to the open-shell nature of their electronic structure. Charge transfer bands of the cation species are stronger and are bathochromically shifted with respect to those of the neutral species due to the greater acceptor ability of the positively charged central carbon atom of the triphenylmethyl moiety. The cationic species 1(+)-3(+) are diamagnetic, as shown by the absence of a signal in the EPR spectrum in acetonitrile solution at room temperature, but they show an intense and unique band in frozen solutions (183 K).

Understanding the fast thermal isomerisation of azophenols in glassy and liquid-crystalline polymers.

The good solubility of azophenols in low molar mass liquid crystals together with the ability of their related polymers to form homogeneous nematic and glassy thin films make such azoderivatives valuable chromophores to get a great variety of photoactivatable systems with fast switching speeds under ambient conditions. In fact, the final applicability of these systems is mainly determined by the thermal cis-to-trans isomerisation rate of the photoactive azophenol used, in other words, by the intimate mechanism the reaction goes through. The kinetico-mechanistic study reported herein shows that the rate of the thermal back reaction for azophenols is very sensitive to the local environment where the azo chromophore is located, mainly to its capability to establish hydrogen bonding with its surroundings. With a proper design, azophenol-based polymers can exhibit thermal isomerisation rates as fast as those of the monomers in solution even without the presence of any solvent.

Photoactuation and thermal isomerisation mechanism of cyanoazobenzene-based liquid crystal elastomers.

4-Alkoxy-4'-cyanoazobenzenes are organic chromophores with great applicability within present nanotechnology. However, the use of such azo dyes for obtaining light-triggered artificial muscle-like actuators remains still unexplored. Achieving further knowledge about the thermal back reaction and isomerisation mechanism for these types of azoderivatives is essential to get photo-actuators with the desired abilities. Despite the push-pull nature of the 4-alkoxy-4'-cyanoazobenzene chromophore, it has been experimentally demonstrated that it isomerises via an inversion mechanism. The opto-mechanics of the prepared elastomeric material has also been investigated. For this system, a maximum opto-mechanical response of ca. 2.5 kPa has been registered, which is independent of the working temperature of the photoactuator.

Supramolecular organization and heterochiral recognition in Langmuir monolayers of chiral azobenzene surfactants.

We study the self-assembly of novel azobenzene-based chiral surfactants at the air/water interface, and find that while the pure enantiomers lack the ability to organize in ordered mesophases, the racemic mixture spontaneously forms a hexatic phase at low lateral pressures, which we detect by means of Brewster angle microscopy. This work provides a unique example of heterochiral recognition in which the racemic monolayer is not only condensed with respect to the pure enantiomers, but causes an ordered mesophase to form. Although hexatic order vanishes at high surface pressures, long-range orientational order is regained for all compositions upon monolayer collapse, which proceeds through the formation of birefringent trilayers with a well-defined lateral microstructure, as revealed by atomic force microscopy.

Programming Positive Mechanofluorescence in Liquid Crystalline Elastomers.

Liquid single crystal elastomers (LSCEs) containing organic fluorophores within their polymeric network are attractive materials to detect forces with simple spectroscopic measurements. Hitherto, all mechanoluminescent LSCEs decrease their emission intensity upon mechanical stimulation; that is, they display negative mechanofluorescence. Such behavior is governed by the mechanically induced approximation of the quenching mesogenic units and the fluorophores. In this work, we propose the integration of fluorescent molecular rotors (FMRs), whose luminescence is not quenched by the mesogens, in LSCEs as a valuable strategy to conceive elastomeric materials programmed with exactly the opposite behavior, i.e., their fluorescence increases upon deformation (positive mechanofluorescence). Specifically, carbazole-indolenine dyes are interesting candidates for this purpose since their luminescence depends mainly on the degree of intramolecular rotation allowed by the local environment. On this basis, the uniaxial deformation of an LSCE, along its anisotropic direction, incorporating such FMRs will place the fluorophores in a more restricted medium, leading to the desired enhanced emission at the macroscale.

Recent advances towards azobenzene-based light-driven real-time information-transmitting materials.

Photochromic switches that are able to transmit information in a quick fashion have attracted a growing interest within materials science during the last few decades. Although very fast photochromic switching materials working within hundreds of nanoseconds based on other chromophores, such as spiropyranes, have been successfully achieved, reaching such fast relaxation times for azobenzene-based photochromic molecular switches is still a challenge. This review focuses on the most recent achievements on azobenzene-based light-driven real-time information-transmitting systems. Besides, the main relationships between the structural features of the azo-chromophore and the thermal cis-to-trans isomerisation, the kinetics and mechanism are also discussed as a key point for reaching azoderivatives endowed with fast thermal back-isomerisation kinetics.

Powder X-ray diffraction as a powerful tool to exploit in organic electronics: shedding light on the first N,N',N''-trialkyldiindolocarbazole.

The first crystal structure of a fully N-alkylated diindolocarbazole derivative, namely, 5,8,14-tributyldiindolo[3,2-b;2',3'-h]carbazole (1, C36H39N3), has been determined from laboratory powder X-ray diffraction (PXRD) data. A complex trigonal structure with a high-volume unit cell of 12987 Å3 was found, with a very long a(=b) [52.8790 (14) Å] and a very short c [5.36308 (13) Å] unit-cell parameter (hexagonal setting). The detailed analysis of the intermolecular interactions observed in the crystal structure of 1 highlights its potential towards the implementation of this core as a semiconductor in organic thin-film transistor (OTFT) devices. Since the molecule has a flat configuration reflecting its π-conjugated system, neighbouring molecules are found to stack atop each other in a slipped parallel fashion via π-π stacking interactions between planes of ca 3.30 Å, with a centroid-centroid distance between the aromatic rings corresponding to the shortest axis of the unit cell (i.e. c). The alkylation of the three N atoms proves to be a decisive feature since it favours the presence of C-H...π interactions in all directions, which strengthens the crystal packing. As a whole, PXRD proves to be a valuable option for the resolution of otherwise inaccessible organic crystal structures of interest in different areas.