Synthesis of Thionated Perylenediimides: State of the Art and First Investigations of an Alternative to Lawesson's Reagent.

Perylenediimides (PDIs) are composed of a central perylene ring, on which are grafted two imide groups at the peri positions. Thionated PDIs are characterized by the substitution of one or more oxygen atoms of these imide functions with sulfur atoms. This structural modification alters the electronic properties with a redshift of the optical absorption accompanied by modification of the charge transport characteristics compared to their non-thionated counterparts. These properties make them suitable candidates for applications in optoelectronic devices, such as organic light-emitting diodes and organic photovoltaics. Moreover, the presence of sulfur atom(s) can favor the promotion of reactive oxygen species production for photodynamic and photothermal therapies. These thionated PDIs can be synthesized through the post-functionalization of PDIs by using a sulfurizing reagent. Nevertheless, the main drawbacks remain the difficulties in adjusting the degree of thionation and obtaining tri- and tetrathionated PDIs. Up to now, this thionation reaction has been described almost exclusively using Lawesson's reagent. In the current study, we present our first investigations into an alternative reagent to enhance selectivity and achieve a greater degree of thionation. The association of phosphorus pentasulfide with hexamethyldisiloxane (Curphey's reagent) clearly demonstrated higher reactivity compared with Lawesson's reagent to attain multi-thionated PDIs.

Recent Advances in Applications of Fluorescent Perylenediimide and Perylenemonoimide Dyes in Bioimaging, Photothermal and Photodynamic Therapy.

The emblematic perylenediimide (PDI) motif which was initially used as a simple dye has undergone incredible development in recent decades. The increasing power of synthetic organic chemistry has allowed it to decorate PDIs to achieve highly functional dyes. As these PDI derivatives combine thermal, chemical and photostability, with an additional high absorption coefficient and near-unity fluorescence quantum yield, they have been widely studied for applications in materials science, particularly in photovoltaics. Although PDIs have always been in the spotlight, their asymmetric counterparts, perylenemonoimide (PMI) analogues, are now experiencing a resurgence of interest with new efforts to create architectures with equally exciting properties. Namely, their exceptional fluorescence properties have recently been used to develop novel systems for applications in bioimaging, biosensing and photodynamic therapy. This review covers the state of the art in the synthesis, photophysical characterizations and recently reported applications demonstrating the versatility of these two sister PDI and PMI compounds. The objective is to show that after well-known applications in materials science, the emerging trends in the use of PDI- and PMI-based derivatives concern very specific biomedicinal applications including drug delivery, diagnostics and theranostics.

Fullerene-Perylenediimide (C60-PDI) Based Systems: An Overview and Synthesis of a Versatile Platform for Their Anchor Engineering.

An overview of the different covalent bonding synthetic strategies of two electron acceptors leading to fullerene-perylenediimide (C60-PDI)-based systems, essentially dyads and triads, is presented, as well as their more important applications. To go further in the development of such electron and photoactive assemblies, an original aromatic platform 5-benzyloxy-3-formylbenzoic acid was synthesized to graft both the PDI dye and the fullerene C60. This new C60-PDI dyad exhibits a free anchoring phenolic function that could be used to attach a third electro- and photoactive unit to study cascade electron and/or energy transfer processes or to obtain unprecedented side-chain polymers in which the C60-PDI dyads are attached as pendant moieties onto the main polymer chain. This C60-PDI dyad was fully characterized, and cyclic voltammetry showed the concomitant reduction process onto both C60 and PDI moieties at identical potential. A quasi-quantitative quenching of fluorescence was demonstrated in this C60-PDI dyad, and an intramolecular energy transfer was suggested between these two units. After deprotection of the benzyloxy group, the free hydroxyl functional group of the platform was used as an anchor to reach a new side-chain methyl methacrylate-based polymer in which the PDI-C60 dyad units are located as pendants of the main polymer chain. Such polymer which associates two complementary acceptors could find interesting applications in optoelectronics and in particular in organic solar cells.

Effect of 2-Methylthiazole Group on Photoinduced Birefringence of Thiazole-Azo Dye Host-Guest Systems at Different Wavelengths of Irradiation.

The photoinduced birefringence behaviors of host-guest systems based on heterocyclic thiazole-azo dyes with different substituents, dispersed into PMMA matrix, were investigated under three excitation wavelengths, i.e., 405 nm, 445 nm or 532 nm. The wavelengths fell on the blue side, near the maximum or on the red side of the absorption bands of trans-azo dyes, respectively. We found that photoinduced birefringence was generated at a similar extent in all studied systems, except the system containing a 2-methyl-5-benzothiazolyl as thiazole-azo dye substituent. For this material, the achieved birefringence value was the highest among the whole series, regardless of the excitation wavelength. Moreover, we identified the optimal irradiation wavelength for efficient birefringence generation and showed that large absorption of excitation light by trans isomer does not account for achieving a significant degree of molecular alignment. The obtained results indicate that thiazole-azo dye with a 2-methyl-5-benzothiazolyl substituent shows promising photoinduced birefringence, and can be considered a dye potentially suitable for optical applications.

Distance Effects of Phenylpiperazine-Containing Methacrylic Polymers on Optical and Structural Properties.

New materials based on methacrylic polymers modified with 1-(4-nitrophenyl)piperazine side chains, differing in the distance of the chromophore from the polymer main chain and/or the separation between the chromophoric units in the chain, are obtained and characterized in terms of their potential applications in optoelectronic devices. The surface, structural, and optical properties of the investigated materials are determined using atomic force microscopy, spectroscopic ellipsometry combined with transmission measurements, Raman and Fourier transform infrared spectroscopy, as well as cyclic voltammetry. The relevant model systems are additionally analyzed with quantum chemical density functional theory calculations in order to enable the generalization of the structure-photophysical property relationships for the optimization of the material features. It is found that the structural modification of the material, relying on the transit of the piperazine moiety away from the main polymer chain, leads to the hypsochromic shift of the absorption spectrum. Moreover, the lowest refractive index values are obtained for the polymer with a distant ethylene group in the side-chains and increased separation between the piperazine units. It was shown that the optical energy band gaps of the investigated piperazine-containing polymers are in the range from 2.73 to 2.81 eV, which reveals their promising potential for the advances in photovoltaics, field effect transistors, or electrochromic devices as an alternative for other widely applied polymer materials.

Effect of UV-Irradiation and ZnO Nanoparticles on Nonlinear Optical Response of Specific Photochromic Polymers.

A series of methacrylic styrylquinoline polymers have been synthesized and characterized by spectroscopic and nonlinear optical (NLO) investigations. The NLO properties of studied polymer compounds in the form of thin films prepared by a spin coating method have been investigated by means of second and third harmonic generation via Maker fringe setup with a laser source at 1064 nm and a pulse duration of 30 ps. The results show strong second harmonic signal dependence on polarization configurations. This second harmonic generation (SHG) response was enhanced by UV-irradiation at 366 nm and doping by ZnO nanoparticles (NPs) (100 nm), while the opposite effect was achieved for a third harmonic generation experiment. Thus, values of second and third order nonlinear susceptibilities were determined by theoretical calculations based on comparative models. The remarkable NLO results presented in this paper expose potential optoelectronic and photonic applications.

Physico-Chemical and Light-Induced Properties of Quinoline Azo-dyes Polymers.

We present investigation of optical and photochromic properties as well as of surface quality of thin films of novel methacrylic polymers with 8-hydroxyquinoline azo-dyes in side-chain. Additionally, thermal stability of polymer powders was examined and their glass transition temperature was determined. Optical properties (extinction coefficient and refractive index) were determined by spectroscopic ellipsometry (SE) combined with absorbance measurements. Photoresponsive behavior was investigated by determination of photoisomerization rates under irradiation with unpolarized 365 nm light, as well as by conduction of holographic grating inscription experiment. Thin film quality was determined by atomic force microscopy (AFM) measurements. Thermal analysis was performed by thermogravimetric (TG), derivative thermogravimetric (DTG) and differential scanning calorimetry (DSC) measurements. We found that optical properties as well as photoisomerization rates of investigated polymers are dependent on the substituent in the para position of the phenyl ring. Surface relief grating inscription was successfully generated only for materials with chromophores containing dimethylamino (N(CH3)2) and methyl (CH3) substituents, but all materials exhibited birefringence grating in the bulk. Surface of most thin films was very smooth, but its quality was impaired by neutral (H) as well as carboxyl (COOH) substituent. Thermal stability of copolymers with side-chain chromophores was improved compared to pure poly(methyl methacrylate) (PMMA).

Coumarin-Containing Polymers for High Density Non-Linear Optical Data Storage.

Optical data storage was performed with various thin polymer films containing coumarin-based derivatives and by using femtosecond laser pulses as well as two-photon absorption processes. Exploring the photodimerization attribute of coumarin derivatives and using appropriate irradiation wavelengths, recording/erasing processes could be carried out in the same area. Second harmonic generation microscopy was used to read the stored information.

Image storage in coumarin-based copolymer thin films by photoinduced dimerization.

We report a technique to encode grayscale digital images in thin films composed of copolymers containing coumarins. A nonlinear microscopy setup was implemented and two nonlinear optical processes were used to store and read information. A third-order process (two-photon absorption) was used to photoinduce a controlled dimer-to-monomer ratio within a defined tiny volume in the material, which corresponds to each recorded bit of data. Moreover, a second-order process (second-harmonic generation) was used to read the stored information, which has been found to be highly dependent upon the monomer-to-dimer ratio.

Second- and third-order nonlinearities of novel push-pull azobenzene polymers.

In this work, the second- and third-order nonlinear optical response of spin-deposited thin films of three different push-pull side chain azobenzene polymers is investigated by the second- and third-harmonic Maker fringes techniques using 30 ps laser pulses at a fundamental wavelength of 1064 nm. Measurements were carried out before and after aligning the chromophores by corona poling of the films, while different polarization configurations have been utilized. Strong dependence of the response upon the structure of the systems has been found, which is related to the different charge transfer within the molecules. The reported findings are compared with already published results.

Reversible two-photon optical data storage in coumarin-based copolymers.

A functionalized polymer film allowing for a complete and straightforward second-harmonic generation (SHG)-assisted high-contrast writing-reading-erasing-writing sequence is proposed. The whole process is supported by the reversible photoinduced dimerization of a coumarin chromophore and enables efficient optical data storage that can be detected only by SHG imaging.