Chiral Truxene-Based Self-Assembled Cages: Triple Interlocking and Supramolecular Chirogenesis.

Incorporating chiral elements in host-guest systems currently attracts much attention because of the major impact such structures may have in a wide range of applications, from pharmaceuticals to materials science and beyond. Moreover, the development of multi-responsive and -functional systems is highly desirable since they offer numerous benefits. In this context, we describe herein the construction of a metal-driven self-assembled cage that associates a chiral truxene-based ligand and a bis-ruthenium complex. The maximum separation between both facing chiral units in the assembly is fixed by the intermetallic distance within the lateral bis-ruthenium complex (8.4 Å). The resulting chiral cavity was shown to encapsulate polyaromatic guest molecules, but also to afford a chiral triply interlocked [2]catenane structure. The formation of the latter occurs at high concentration, while its disassembly could be achieved by the addition of a planar achiral molecule. Interestingly the planar achiral molecule exhibits induced circular dichroism signature when trapped within the chiral cavity, thus demonstrating the ability of the cage to induce supramolecular chirogenesis.

Chloride Binding Modulated by Anion Receptors Bearing Tetrazine and Urea.

Modulation and fine-tuning of the strength of weak interactions to bind anions are described in a series of synthetic receptors. The general design of the receptors includes both a urea motif and a tetrazine motif. The synthetic sequence towards three receptors is detailed. Impacts of H-bond strength and linker length between urea and tetrazine on chloride complexation are studied. Binding properties of the chloride anion are examined in both the ground and excited states using a panel of analytical methods (NMR spectroscopy, mass spectrometry, UV/Visible spectroscopies, and fluorescence). A ranking of the receptors by complexation strength has been determined, allowing a better understanding of the structure-properties relationship on these compounds.

Dynamics of the energy transfer involved in a diarylethene-perylenebisimide dyad: comparison between the molecule and the nanoparticle level.

Photochromic materials are widely used to achieve fluorescence photoswitching. Understanding the energy transfer processes occurring in these systems would be an advantage for their use and better optimization of their properties. In this scope, we studied a diarylethene-perylenebisimide (DAE-PBI) dyad that presents a bright red emission and a large ON-OFF contrast, both in solution and in an aqueous suspension of nanoparticles (NPs). Using ultrafast transient absorption spectroscopy, the excited state dynamics was characterized for this dyad in THF solution and compared to its behavior in NPs state. An efficient energy transfer process between the PBI fluorophore and the DAE photochromic unit in its closed form was demonstrated, occurring in a few hundreds of femtoseconds.

Polymerization of tetrazine-substituted diacetylenes as aggregates in suspension.

Polydiacetylenes (PDAs) are conjugated polymers that have been widely exploited for their chromogenic and fluorogenic transitions upon exposure to external stimuli and biomolecules of interest. Herein, we propose a comparative study of the polymerization dynamics of two diacetylene derivatives, TzDA1 and TzDA2, in the form of aggregates in suspension prepared by reprecipitation method from organic solvents in water, varying the diacetylene concentration and solvent proportions, and sonication in water, varying the time and temperature. Both derivatives bear a tetrazine fluorophore, which serves both to increase the fluorescence quantum yield of the system and to track the polymerization by fluorescence quenching exclusively by the blue-PDA, and differ by the chain termination. It was shown that adding a butyl ester function in TzDA2 to a simple urethane (TzDA1) influences the polymerizability and kinetics of polymerization of the aggregates in suspension. In addition, we showed that also the preparation method and preparation conditions do have an influence on the polymerization dynamics, suggesting that a careful study of these properties should be carried out before investigating the applications of such objects.

Circularly Polarized Luminescence and Circular Dichroism of Bichromophoric Difluoroboron-ß-diketonates: Inversion and Enhanced Chirality Based on Spatial Arrangements and Self-Assembly.

We synthesized two bichromophoric difluoroboron-ß-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge (para and meta (R/S)-CyDFB). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores.

Novel D-A chromophores with condensed 1,2,4-triazine system simultaneously display thermally activated delayed fluorescence and crystallization-induced phosphorescence.

Control of photophysical properties is crucial for the continued development of electroluminescent devices and luminescent materials. Preparation and study of original molecules uncovers design rules towards efficient materials and devices. Here we have prepared 7 new compounds based on the popular donor-acceptor design used in thermally activated delayed fluorescence emitters. We introduce for the first time benzofuro[3,2-e]-1,2,4-triazine and benzothieno[3,2-e]-1,2,4-triazine acceptors which were connected to several common donors: phenoxazine, phenothiazine, carbazole and 3,6-di-tert-butylcarbazole. DFT calculations, and steady-state and time-resolved photophysical studies were conducted in solution and in solid states. While derivatives with azine moieties are non-emissive in any form, the compounds comprising 3,6-di-tert-butylcarbazole display TADF in all cases. More interestingly, the two derivatives substituted with a carbazole donor are TADF active when dispersed in a polymer matrix and phosphorescent at room temperature in neat films (microcrystalline form).

Multi-Directional Mechanofluorochromism of Acetyl Pyrenes and Pyrenyl Ynones.

A series of acetyl pyrenes and pyrenyl ynones with and without tert-butyl groups showed distinct mechanofluorochromism (MFC). Four pairs of polymorphic solids were found out of six compounds and interestingly, each of them showed hypsochromic, bathochromic or off-to-on MFC. The MFC properties were rationalized by categorizing the packing schemes into herringbone, sandwich, beta and gamma motifs depending on the relative contributions of C⋅⋅⋅C (or π-π) against C⋅⋅⋅H contacts. The bulky tert-butyl and trimethylsilyl groups served not only to reduce the number of aggregation patterns but also to prohibit the complete back reactions in solid state. Our results suggest that the simple pyrene derivatives may be promising candidates for a novel group of mechanically-sensitive materials.

Enhanced mechano-responsive fluorescence in polydiacetylene thin films through functionalization with tetrazine dyes: photopolymerization, energy transfer and AFM coupled to fluorescence microscopy studies.

The development of mechano-responsive fluorescent materials is essential for the design and construction of reliable and versatile sensors for mechanical stress. Herein, novel energy transfer-based systems with tetrazine fluorophore and a polydiacetylene (PDA) backbone are synthesized and studied comparatively to a simple polydiacetylene in the form of thin films. Their photopolymerization properties, energy transfer efficiencies and fluorescent response to nanoscale mechanical stimulation are assessed. It is pointed out that the self-assembling group on the PDA chain influences the geometrical arrangement of the chains and the film morphology and, as a consequence, the efficiency and kinetics of polymerization and the energy transfer efficiency. Moreover, we show that the strategy of introducing tetrazine fluorophore provides a new effective route of improving force detectability by fluorescence using polydiacetylenes as mechano-responsive units.

Exciton Interactions, Excimer Formation, and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers.

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF2 dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional 1 H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.

Intertwined Detection and Recognition Roles of Tetrazine in Synergistic Anion-π and H-bond Based Anion Receptor.

The intrinsic properties of tetrazine as a π-anion receptor and as an on/off recognition probe merged with H-bond ability of an urea motif into a single architecture constitutes a new generation of well-defined anion receptors. Complexation properties directly benefit from the dual and synergistic contribution of tetrazine and urea. In this study, we report on the synthesis and assessment of binding properties to anions of diverse geometries. Association constants have been predicted by theoretical calculations and evaluated by multiple and complementary experimental techniques including electrospray-mass tandem spectroscopy, NMR, UV-visible, steady state fluorescence spectroscopies and time resolved fluorescence. These results provide the basis for a better understanding of both the complexation and the anion-dependent quenching mechanism.

Mechanofluorochromism of pyrene-derived amidophosphonates.

Aiming to develop a library of organic mechanofluorochromic (MFC) materials, solid-state emission properties of pyrene-derivatives with amidophosphonate groups (diethyl 1-(pyrene-1-carboxamido)alkylphosphonates, alkyl: methyl, isopropyl, phenyl) were investigated. All of these compounds were found to show strong blue fluorescence, and blue-to-green emission shift was identified upon grinding. Monomer and several excimer emissive species were identified by steady-state and time-resolved fluorescence investigations. The characteristic green-to-blue thermal back reaction was observed even at room temperature without additives, which would be related to the flexibility of side groups for molecular rearrangement. We here demonstrated that the pyrene-derived compounds can be attractive platforms to host MFC properties.

Photoreduction of triplet thioxanthone derivative by azolium tetraphenylborate: a way to photogenerate N-heterocyclic carbenes.

Although N-heterocyclic carbenes (NHCs) have brought profound changes in catalytic organic synthesis, their generation generally requires an inert atmosphere and harsh conditions. To overcome these limitations, an air-stable NHC photogenerator has been developed involving two mild components: 1,3-bis(mesityl)imidazolium tetraphenylborate (IMesH+BPh4-) and electronically excited isopropylthioxanthone (ITX). In this study, the photochemical mechanism is investigated via the accurate identification of the transient species and photoproducts. Electron transfer reaction between the excited triplet state of ITX and BPh4- is demonstrated as being the primary photochemical step. Nanosecond laser spectroscopy shows an efficient quenching and the formation of the expected ITX radical anion. The oxidized borane species is not observed, suggesting that this short-lived species could dissociate very rapidly to give the phenyl radical - successfully identified using electron paramagnetic resonance - and triphenylborane. As regards the final photoproducts, 1H and 13C NMR spectroscopies support the formation of the targeted NHC, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), suggesting the occurrence of a subsequent proton transfer reaction between ITX radical anion and imidazolium cation (IMesH+). Gas chromatography-mass spectrometry reveals three other products: biphenyl, isopropylthioxanthene and ITX. Their formation can be reconciled with a 2-step mechanism of photoinduced electron/proton transfer reactions. 11B NMR spectroscopy demonstrates that the main organoboron photoproduct is diphenylborinic acid formed by oxidation of BPh3. Due to its Lewis acidity, Ph2BOH can react with IMes to yield an NHC-boron adduct.

Synthesis, regioselective aerobic Pd(ii)-catalyzed C-H bond alkenylation and the photophysical properties of pyrenylphenylpyrazoles.

This paper reports the synthesis, regioselective aerobic Pd(ii)-catalyzed C-H bond alkenylation and the photophysical properties of pyrenylphenylpyrazoles.

Giant Amplification of Photoswitching by a Few Photons in Fluorescent Photochromic Organic Nanoparticles.

Controlling or switching the optical signal from a large collection of molecules with the minimum of photons represents an extremely attractive concept. Promising fundamental and practical applications may be derived from such a photon-saving principle. With this aim in mind, we have prepared fluorescent photochromic organic nanoparticles (NPs), showing bright red emission, complete ON-OFF contrast with full reversibility, and excellent fatigue resistance. Most interestingly, upon successive UV and visible light irradiation, the NPs exhibit a complete fluorescence quenching and recovery at very low photochromic conversion levels (<5 %), leading to the fluorescence photoswitching of 420±20 molecules for only one converted photochromic molecule. This "giant amplification of fluorescence photoswitching" originates from efficient intermolecular energy-transfer processes within the NPs.

Aerobic palladium(II)-catalyzed dehydrogenative heck reaction in the synthesis of pyrenyl fluorophores. a photophysical study of ß-pyrenyl acrylates in solution and in the solid state.

An aerobic dehydrogenative Heck reaction of pyrene (1a) and 2,7-di-tert-butylpyrene (1b) with ethyl acrylate is reported. The reaction is catalyzed by a Pd(OAc)2/4,5-diazafluoren-9-one (DAF) system and takes place in acetic or pivalic acid as solvents at 110-130 °C. The reaction of 1a afforded a 6:1 mixture of C-1- and C-4-alkenylated pyrenes (2a and 3a, respectively) in 71% yield. In the case of 1b, only a C-4-substituted product (3b) was formed in 46% yield. Compounds 2a and 3a,b exhibited fluorescence in solution and in the solid state. In chloroform and THF solution the fluorescence maxima were in the range of 440-465 nm, and quantum yields decreased in the order 2a > 3a> 3b. In the solid state, 3a,b showed blue-green fluorescence (ΦF = 0.26 and 0.14, respectively), whereas 2a emitted yellow-green fluorescence) (ΦF = 0.35). Besides blue-emitting monomers, the presence of green-emitting aggregated species (preformed dimers) in the crystals of 3a,b and red-emitting dynamic excimers in the crystals of 2a has been demonstrated. Single-crystal X-ray diffraction analyses of 2a and 3b confirmed π-stacking of pyrenyl moieties in the crystals of the former and the absence of stacking in the crystals of the latter compound.

Friedel-Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid.

Friedel-Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates promoted by trifluoromethanosulfonic acid afforded diethyl 1-(pyrene-1-carbothioamido)alkylphosphonates in 83-94% yield. These compounds were transformed, in 87-94% yield, into the corresponding diethyl 1-(pyrene-1-carboxamido)alkylphosphonates by treatment with Oxone(®). 1-(Pyrene-1-carboxamido)methylphosphonic acid was obtained in a 87% yield by treating the corresponding diethyl phosphonate with Me3Si-Br in methanol. All of the synthesized amidophosphonates were emissive in solution and in the solid state. The presence of a phosphonato group brought about an approximately two-fold increase in solution fluorescence quantum yield in comparison with that of a model N-alkyl pyrene-1-carboxamide. This effect was tentatively explained by stiffening of the amidophosphonate lateral chain which was caused by the interaction (intramolecular hydrogen bond) of phosphonate and amide groups. The synthesized phosphonic acid was soluble in a biological aqueous buffer (PBS, 0.01 M, pH 7.35) and was strongly emissive under these conditions (λem = 383, 400 nm, τ = 18.7 ns, ΦF > 0.98). Solid-state emission of diethyl 1-(pyrene-1-carboxamido)methylphosphonate (λmax = 485 nm; ΦF = 0.25) was assigned to π-π aggregates, the presence of which was revealed by single-crystal X-ray diffraction analysis.

Photoswitchable interactions between photochromic organic diarylethene and surface plasmon resonance of gold nanoparticles in hybrid thin films.

Hybrid materials combining gold nanoparticles (GNP) of variable diameter and an organic thin layer of photochromic diarylethenes were achieved. Solid-state photoswitching based on ring-closure/ring-opening reaction was carried out under alternate UV and visible irradiations. In addition to the spectral changes due to the photochromism itself, the surface plasmon resonance related to the GNP is significantly modified, influenced by a photoinduced change in the refractive index of its environment. These two contributions were sorted out, showing the possibility of probing a photochromic switch by following the plasmon band. The shape change of the plasmon band was consistently compared to calculations based on the Mie theory. Additionally, with one given diarylethene compound, both UV-visible spectroscopy and surface enhanced Raman scattering (SERS) spectroscopy showed an acceleration of the ring-opening photochromic reaction in the presence of GNP.

Fluorescent carboxylic and phosphonic acids: comparative photophysics from solution to organic nanoparticles.

Phosphonic and carboxylic fluorescent nanoparticles have been fabricated by direct reprecipitation in water. Their fluorescence properties strongly differ from those of the corresponding esters where strong H-bonding formation is prohibited. Comparative experiments between the two acid derivatives, differing only in their acid functions while keeping the same alkyl chain, have evidenced the peculiar behavior of the phosphonic acid derivative compared to its carboxylic analog. A dramatic emission quenching for the phosphonic acid in aprotic toluene could be observed while a fivefold increase in the fluorescence signal was observed for molecules assembled as nanoparticles. Such properties have been attributed on the theoretical basis to the formation of folded conformers in solution, leading to deactivation of the radiative excited state through intramolecular H-bonding. These studies evidence for the first time through time-resolved fluorescence measurements the stronger H-donating character of phosphonic acids compared to the carboxylic ones, and provide information on the degree of structural heterogeneity within the nanoparticles. They should pave the way for the rational fabrication of chelating acid fluorophores, able to complex metal oxides to yield stiff hybrid magnetofluorescent nanoparticles which are attracting considerable attention in the growing fields of bimodal imaging and vectorization applications.

White fluorescence from core-shell silica nanoparticles.

Into the white: Encapsulation of a naphthalimide moiety in the core of silica nanoparticles afforded nanospheres with a strong green excimeric emission. Together with the blue emission of the monomeric naphthalimide and the yellow fluorescence of the tetrazine acceptor on the outer shell, the added contributions provide intense white fluorescence upon 330 nm UV excitation.

Design and property investigation on a five-interaction-based fluorescent anion receptor clip.

A molecular clip combining a doubly substituted fluorescent anion-π donor probe and two flexible arms bearing H-bond motifs constitutes a new generation of anion receptors. Five simultaneous non-covalent interactions are highlighted by theoretical complexation studies with five different anions. A large range of analytical techniques (electrospray-tandem mass spectrometry, NMR, UV-visible, steady-state and time-resolved fluorescence) were deployed to evaluate the stoichiometry and association constants with the selected anions. The photophysical and anion-π donor properties of the tetrazine ring allowed fine characterization of the binding properties of the ligand. Based on previously published results, an anti-cooperativity effect in non-covalent interactions was demonstrated.