First Example of a Heptazine-Porphyrin Dyad; Synthesis and Spectroscopic Properties.

We have prepared the first example of a porphyrin linked to an heptazine photoactive antenna. The two entities, linked with an alkyl spacer, demonstrate the activity of both active moieties. While they behave electrochemically independantly, on the other hand the spectroscopy shows the existence of energy transfer between both partners.

Tetrazine molecules as an efficient electronic diversion channel in 2D organic-inorganic perovskites.

Taking advantage of an innovative design concept for layered halide perovskites with active chromophores acting as organic spacers, we present here the synthesis of two novel two-dimensional (2D) hybrid organic-inorganic halide perovskites incorporating for the first time 100% of a photoactive tetrazine derivative as the organic component. Namely, the use of a heterocyclic ring containing a nitrogen proportion imparts a unique electronic structure to the organic component, with the lowest energy optical absorption in the blue region. The present compound, a tetrazine, presents several resonances between the organic and inorganic components, both in terms of single particle electronic levels and exciton states, providing the ideal playground to discuss charge and energy transfer mechanisms at the organic/inorganic interface. Photophysical studies along with hybrid time-dependent DFT simulations demonstrate partial energy transfer and rationalise the suppressed emission from the perovskite frame in terms of different energy-transfer diversion channels, potentially involving both singlet and triplet states of the organic spacer. Periodic DFT simulations also support the feasibility of electron transfer from the conduction band of the inorganic component to the LUMO of the spacer as a potential quenching mechanism, suggesting the coexistence and competition of charge and energy transfer mechanisms in these heterostructures. Our work proves the feasibility of inserting photoactive small rings in a 2D perovskite structure, meanwhile providing a robust frame to rationalize the electronic interactions between the semiconducting inorganic layer and organic chromophores, with the prospects of optimizing the organic moiety according to the envisaged application.

Fluorescent Liquid Tetrazines.

Tetrazines with branched alkoxy substituents are liquids at ambient temperature that despite the high chromophore density retain the bright orange fluorescence that is characteristic of this exceptional fluorophore. Here, we study the photophysical properties of a series of alkoxy-tetrazines in solution and as neat liquids. We also correlate the size of the alkoxy substituents with the viscosity of the liquids. We show using time-resolved spectroscopy that intersystem crossing is an important decay pathway competing with fluorescence, and that its rate is higher for 3,6-dialkoxy derivatives than for 3-chloro-6-alkoxytetrazines, explaining the higher fluorescence quantum yields for the latter. Quantum chemical calculations suggest that the difference in rate is due to the activation energy required to distort the tetrazine core such that the nπ*S1 and the higher-lying ππ*T2 states cross, at which point the spin-orbit coupling exceeding 10 cm-1 allows for efficient intersystem crossing to occur. Femtosecond time-resolved anisotropy studies in solution allow us to measure a positive relationship between the alkoxy chain lengths and their rotational correlation times, and studies in the neat liquids show a fast decay of the anisotropy consistent with fast exciton migration in the neat liquid films.

Characterization and Electronic Properties of Heptazine Layers: Towards Promising Interfacial Materials for Organic Optoelectronics.

For the first time, an original compound belonging to the heptazine family has been deposited in the form of thin layers, both by thermal evaporation under vacuum and spin-coating techniques. In both cases, smooth and homogeneous layers have been obtained, and their properties evaluated for eventual applications in the field of organic electronics. The layers have been fully characterized by several concordant techniques, namely UV-visible spectroscopy, steady-state and transient fluorescence in the solid-state, as well as topographic and conductive atomic force microscopy (AFM) used in Kelvin probe force mode (KPFM). Consequently, the afferent energy levels, including Fermi level, have been determined, and show that these new heptazines are promising materials for tailoring the electronic properties of interfaces associated with printed electronic devices. A test experiment showing an improved electron transfer rate from a tris-(8-hydroxyquinoline) aluminum (Alq3) photo-active layer in presence of a heptazine interlayer is finally presented.

A straightforward synthesis of a new family of molecules: 2,5,8-trialkoxyheptazines. Application to photoredox catalyzed transformations.

We have prepared several 2,5,8-trialkoxyheptazines starting from the soluble precursor 2,5,8-tris(3,5-diethylpyrazolyl)-heptazine. We present their synthesis along with their promising spectroscopic and electrochemical properties, which demonstrate large band gaps and high reduction potentials altogether. Subsequently, we provide a short assessment of the promising ability of one of these molecules to perform catalytic oxidation test-reactions.

Renewing accessible heptazine chemistry: 2,5,8-tris(3,5-diethyl-pyrazolyl)-heptazine, a new highly soluble heptazine derivative with exchangeable groups, and examples of newly derived heptazines and their physical chemistry.

We have prepared 2,5,8-tris(3,5-diethyl-pyrazolyl)-heptazine, the first highly soluble heptazine derivative possessing easily exchangeable leaving groups. We present its original synthesis employing mechanochemistry, along with a few examples of its versatile reactivity. It is, in particular, demonstrated that the pyrazolyl leaving groups can be replaced by several secondary or primary amino substituents or by three aryl- or benzyl-thiol substituents. In addition to being a synthetic platform, 2,5,8-tris(3,5-diethyl-pyrazolyl)-heptazine is fluorescent and electroactive, and its attractive properties, as well as those of the derived heptazines, are briefly presented.

Photocatalytic efficacy of supported tetrazine on MgZnO nanoparticles for the heterogeneous photodegradation of methylene blue and ciprofloxacin.

MgZnO@SiO2-tetrazine nanoparticles were synthesized and their photocatalytic efficiency was demonstrated in the decomposition of ciprofloxacin and methylene blue (MB). This new heterogeneous nanocatalyst was characterized by FT-IR, XRD, UV-vis, DRS, FE-SEM, ICP, and CHN. Distinctive variables including photocatalyst dose, pH, and degradation time were investigated. Up to 95% photodegradation was gained under the optimum conditions (20 mg photocatalyst, 3.5 ppm MB, pH 9) by using MgZnO@SiO2-tetrazine nanoparticles after 20 min. An elementary kinetic study was carried out, and a pseudo-first-order kinetic with a reasonably high rate-constant (0.068 min-1) was derived for the MB decay. Photoluminescence (PL) studies confirmed that the photocatalytic activity of MgZnO@SiO2-tetrazine was almost consistent with the Taugh plots. Thus, it can be envisaged that the photocatalytic activity is closely related to the optical absorption. Furthermore, a photoreduction mechanism was suggested for the degradation process. Addition of scavengers and some mechanistic studies also revealed that O2˙- is the original radical accounting for the degradation of MB, considering this latter compound as a model type pollutant. Finally, efficacy of the present photocatalytic process was assessed in the degradation of ciprofloxacin as a model drug under the optimum reaction conditions.

Synthesis and Characterization of New Fluorinated Tetrazines Displaying a High Fluorescence Yield.

Following the case of tetrazines substituted with perfluorinated alkyl chains, separated by two methylene groups from the tetrazine core, a new series of analogous tetrazines, but featuring only one methylene group between the fluorescent core and the perfluorinated chain, have been synthesized, and their photo-physical properties investigated. Their fluorescence quantum yields in acetonitrile are in same range than chloroalkoxytetrazines, which make them interesting candidates for light emission. Surprisingly, the quantum yields are lower with one methylene group, rather than two methylene groups separating the fluorinated chain from the emitting core, in the case of unsymmetrical compounds, while they are superior in the case of symmetrical ones. This unusual observation is discussed in the article.

First Occurrence of Tetrazines in Aqueous Solution: Electrochemistry and Fluorescence.

The photophysical and electrochemical properties of tetrazines substituted by linear 2,3-naphtalimide antennas and/or adamantane groups specifically dedicated to host-guest interactions with cyclodextrins are studied both in organic and aqueous media. In acetonitrile solvent, the reduction potential of tetrazine leading to the anion radical is shifted, depending on the electron-withdrawing power of the substituent of the tetrazines. Due to the hydrophobic character of these compounds, their solubilization in aqueous solution is achieved successively in presence of either ß-cyclodextrins or gold nanoparticules modified by ß-cyclodextrins. We demonstrate that the formation of the inclusion compound tetrazine-cyclodextrin allows the solubilization of the tetrazines in aqueous solution. The supramolecular assemblies obtained in water retain tetrazine's emission properties, yielding a yellow fluorescence.

Two-Dimensional Perovskite Activation with an Organic Luminophore.

A great advantage of the hybrid organic-inorganic perovskites is the chemical flexibility and the possibility of a molecular engineering of each part of the material (the inorganic part and the organic part respectively) in order to improve or add some functionalities. An adequately chosen organic luminophore has been introduced inside a lead bromide type organic-inorganic perovskite, while respecting the two-dimensional perovskite structure. A substantial increase of the brilliance of the perovskite is obtained. This activation of the perovskite luminescence by the adequate engineering of the organic part is an original approach, and is particularly interesting in the framework of the light-emitting devices such as organic light-emitting diodes (OLEDs) or lasers.

Photostability of 2D Organic-Inorganic Hybrid Perovskites.

We analyze the behavior of a series of newly synthesized (R-NH3)2PbX4 perovskites and, in particular, discuss the possible reasons which cause their degradation under UV illumination. Experimental results show that the degradation process depends a lot on their molecular components: not only the inorganic part, but also the chemical structure of the organic moieties play an important role in bleaching and photo-chemical reaction processes which tend to destroy perovskites luminescent framework. In addition, we find the spatial arrangement in crystal also influences the photostability course. Following these trends, we propose a plausible mechanism for the photodegradation of the films, and also introduced options for optimized stability.

Lumicyano™: a new fluorescent cyanoacrylate for a one-step luminescent latent fingermark development.

Latent fingermarks developed by cyanoacrylate fuming often lack contrast; therefore further enhancement is required, such as dye staining. This second step is part of the conventional detection sequences performed by forensics practitioners. Dye-staining or powder dusting aims at improving contrast and at increasing the legibility of details, yet their use may at times be limited. Indeed powder dusting may not be effective due to unexpected adherence to the background, and poor affinity to the cyanoacrylate. In the same way staining processes can dye a whole semi-porous surface or may wash the marks. To avoid that second step, a new luminescent cyanoacrylate (Lumicyano™) which allows one-step development without changing the fuming chamber settings (80% humidity rate, 120°C fuming temperature) was developed and assessed. This study aimed at comparing Lumicyano™ to a conventional two-step process. A detailed sensitivity study was conducted on glass slides, as well as the processing of various non-porous and semi-porous substrates, usually considered as problematic for a dye staining step. The results indicate that Lumicyano™ detects fingermarks with equal or better sensitivity and ridge details than currently used cyanoacrylate. Secondly in luminescent mode, good ridges clarity and excellent contrast are observed, even if Lumicyano™ is sometimes less bright than the two-step process. Furthermore, conventional enhancement can still be carried out if needed. As a conclusion, Lumicyano™ makes it possible to avoid an enhancement step which can be detrimental to further examinations, particularly on rough or semi-porous surfaces.