C3-Symmetric Luminescent Diketone with Amido-Linkage as a Polymorphic Fluorescence Emitter.

The study introduces a novel C3-symmetric ß-diketone compound, BTA-D3, and its monomeric counterpart, D, with a focus on their synthetic procedure, photophysical properties and aggregation behavior. Both compounds exhibit characteristic absorption and weak fluorescence in solution, with BTA-D3 displaying higher absorption coefficients due to its larger number of diketone units. Density Functional Theory (DFT) calculations suggest increased co-planarity of diketone groups in BTA-D3. A significant finding is the Aggregation-Induced Emission (AIE) property of BTA-D3, as its fluorescence intensity increases dramatically when exposed to specific solvent ratios. The AIE behavior is attributed to intermolecular excitonic interaction between BTA-D3 molecules in self-organized aggregates. We also studied fluorescence anisotropy of BTA-D3 and D. Despite its larger size, BTA-D3 showed reduced anisotropy values because of efficient intramolecular energy migration among three diketone units. Furthermore, BTA-D3 demonstrates unique polymorphism, yielding different emission colors and structures depending on the solvent used. A unique approach is presented for promoting the growth of self-organized aggregate structures via solvent evaporation, leading to distinct fluorescence properties. This research contributes to the understanding of C3-symmetric structural molecules and provides insights into strategies for controlling molecular alignment to achieve diverse fluorescence coloration in molecular materials.

Mechanofluorochromism and self-recovery of alkylsilylpyrene-1-carboxamides.

A family of (alkylsilyl)pyrene-1-carboxamides exhibits similar mechanofluorochromic responses upon grinding. However, their spontaneous fluorescence recovery processes are distinct despite their similarity in chemical structures and crystal packings. Fluorescence spectroscopy, crystallography, and nanomechanical tests revealed that the chromic direction is dominated by the packing motif, while the fluorescence recovery is driven by the intermolecular interactions and the reversibility of deformation.

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.

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.

Tuning the photochemical ring-closing reaction efficiency in diarylethene-based photoswitches through engineering of internal charge transfer.

The photochemical quantum yield is one of the key features for a photoswitch and its tuning is challenging. In an attempt to tackle this issue within the popular diarylethene-based switches, we have explored the potential to use internal charge transfer (CT), a readily controllable parameter, for an effective modulation of the photocyclization quantum yield. For this, a homogeneous family of terarylenes, a sub-class of diarylethenes, with different CT characters, but the same photochromic core was designed and its photochromic properties were fully investigated. A clear correlation was found between the cyclization quantum yield and the CT character of the switch. More precisely, almost linear relationships were established between the ring-closing quantum yield and (i) the electron density variation accompanying the S0 → S1 transition and (ii) the percentage of LUMO on the reactive carbon atoms. Such a correlation was rationalized by a joint spectroscopic analysis and theoretical modelling of both ground and first excited states, introducing the concept of "early" or "late" photochromes. Encouragingly, such a potentally predictive model also seemed relevant when applied to some other diarylethene-based switches reported in the literature.

Fur glowing under ultraviolet: in situ analysis of porphyrin accumulation in the skin appendages of mammals.

Examples of photoluminescence (PL) are being reported with increasing frequency in a wide range of organisms from diverse ecosystems. However, the chemical basis of this PL remains poorly defined, and our understanding of its potential ecological function is still superficial. Among mammals, recent analyses have identified free-base porphyrins as the compounds responsible for the reddish ultraviolet-induced photoluminescence (UV-PL) observed in the pelage of springhares and hedgehogs. However, the localization of the pigments within the hair largely remains to be determined. Here, we use photoluminescence multispectral imaging emission and excitation spectroscopy to detect, map, and characterize porphyrinic compounds in skin appendages in situ. We also document new cases of mammalian UV-PL caused by free-base porphyrins in distantly related species. Spatial distribution of the UV-PL is strongly suggestive of an endogenous origin of the porphyrinic compounds. We argue that reddish UV-PL is predominantly observed in crepuscular and nocturnal mammals because porphyrins are photodegradable. Consequently, this phenomenon may not have a specific function in intra- or interspecific communication but rather represents a byproduct of potentially widespread physiological processes.

Nondestructive All-Optical Readout through Photoswitching of Intramolecular Excimer Emission.

We report the first intramolecular excimer photoswitching induced by molecular motion within a dithienylethene (DTE) molecule without destructive readout. The photochromic compound DTE bears two pyrene chromophores, judiciously positioned to face each other in the DTE's open form. The close proximity of the pyrenes in the open form is confirmed by NMR experiments and geometry optimization. Intense pyrene excimer luminescence is recorded, upon both one- and two-photon excitation (OPE and TPE). The photocyclization reaction of the DTE core induces a molecular motion of one pyrene moiety which thus prevents the possibility of formation of an excimer. Our DTE-based pyrene is stable upon TPE irradiation and shows a high photocyclization quantum yield. Such property specifications allow us to report the original nondestructive readout fluorescence by alternating exposure to OPE and TPE.

Competitive Photoisomerization and Energy Transfer Processes in Fluorescent Multichromophoric Systems.

Multichromophoric systems showing both fluorescence and photoisomerization are fascinating, with complex interchromophoric interactions. The experimental and theoretical study of a series of compounds, bearing a variable number of 4-dicyanomethylene-2-tert-butyl-6-(p-(N-(2-azidoethyl)-N-methyl)aminostyryl)-4H-pyran (DCM) units are reported. The photophysical properties of multi-DCM derivatives, namely 2DCM and 3DCM, were compared to the single model azido-functionalized DCM, in the E and Z isomers. The (EE)-2DCM and (EEE)-3DCM were synthesized via the click reaction. Steady-state spectroscopy and photokinetics experiments under UV or visible irradiation indicated the presence of intramolecular energy transfer processes among the DCM units. Homo- and hetero-energy transfer processes between adjacent chromophores were confirmed by fluorescence anisotropy and decays. Molecular dynamics simulations for 2DCM were carried out and analyzed using a Markov state model, providing geometrical parameters (orientation and distance between chromophores) and energy transfer efficiency. This work contributes to a better understanding and rationalization of multiple energy transfer processes occuring within multichromophoric systems.

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.

Mechanofluorochromic Difluoroboron ß-Diketonates Based Polymer Composites: Toward Multi-Stimuli Responsive Mechanical Stress Probes.

Developing mechano-responsive fluorescent polymers that exhibit distinct responses to distinct mechanical stresses requires a careful design of the fluorophore in order to tune its interactions with the polymer. A series of mechanofluorochromic (MFC) polymer composites are prepared by dispersing difluoroboron diketonates complexes with various alkyl side-chain lengths (DFB-alkyl) in linear low-density polyethylene. Observation of the resulting polymer composites under a microscope reveals different aggregate sizes of the three DFB-alkyls, thus confirming the functionalization by alkyl side chains as a powerful approach to control the aggregation process in a polymer. Besides, the three polymer composite samples are shown to be sensitive to both stretching and scratching, thereby consisting in the first reported example of MFC polymer responding to these two distinct mechanical stimuli. To establish a structure-property relationship, the strategy consisted in applying controlled tensile or friction forces while simultaneously monitoring fluorescence changes. Interestingly, the intensity of the MFC response to both stretching and scratching depends on the alkyl chain length and thus on the aggregation properties of the fluorophore. According to a time-resolved fluorescence study, the emission is found to originate from different species following the type of applied stress (tensile or friction force).

Photoisomerization of a 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran analog dye: a combined photophysical and theoretical investigation.

A combination of experimental and theoretical investigations of a photoisomerizable analog of 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) dye molecule is presented. We provide evidence that the 4 main isomers and conformers of DCM contribute to its photochemical and photophysical processes. The absorption and emission spectra, as well as time-resolved fluorescence experimental results, are discussed and compared to DFT/TDDFT calculations. The E ↔ Z isomerization is induced photochemically, whereas the s-cis ↔ s-trans conformational interconversion is a thermal process which may also happen during irradiation. The photoreaction pathways from the first excited state down to the ground state are shown to be mediated by two conical intersections, as revealed using spin-flip TDDFT calculations. The rationalization of these isomerization schemes provides important insights into the photophysical properties of DCM, responsible for its photoswitchable fluorescence.

Cyclometalated Rhodium and Iridium Complexes Containing Masked Catecholates: Synthesis, Structure, Electrochemistry, and Luminescence Properties.

Two neutral cyclometalated rhodium and iridium coordination assemblies [(F2ppy)2M(η-Cat)], M = Rh, (2) and M = Ir, (3) (F2ppy: 2,4-difluorophenylpyridine), displaying a masked catecholate (η-Cat = η-O∧O) are described. The catecholate ligand is π-bonded to an organometallic Cp*Ru(II) moiety. The latter brings stability to the whole system in solution and suppresses the formation of the related paramagnetic semiquinone complex. The determination of the molecular structure of the iridium complex [(F2ppy)2Ir(η-Cat)] (3) corroborates the formation of the target compound and reveals the generation of a rare two-dimensional (2D) honeycomb supramolecular architecture in the solid state, in which the Δ-enantiomer self-assembles with the Λ-enantiomer through encoded π-π interactions among individual units. The electrochemistry of complexes 2 and 3 was investigated and showed that reduction occurs at very negative potentials (∼-2.2 V versus saturated calomel electrode (SCE)), while oxidation of the cyclometalated Rh and Ir centers occurs at 0.8 and 0.86 V. In contrast to complexes with 1,2-dioxolene chelates, which are nonemissive, the heterodinuclear diamagnetic complexes 2 and 3 were found to be emissive at room temperature both in solution and in the solid state. Moreover, at 77 K in a solid state, both compounds display opposite emission behavior, for instance, complex 3 displays a blue-shifted emission, while rhodium compound 2 exhibits red-shifted emission to lower energy.

4,4'-Dimethylazobenzene as a chemical actinometer.

Chemical actinometers are a useful tool in photochemistry, which allows to measure the photon flux of a light source to carry out quantitative analysis on photoreactions. The most commonly employed actinometers so far show minor drawbacks, such as difficult data treatment, parasite reactions, low stability or impossible reset. We propose herewith the use of 4,4'-dimethylazobenzene as a chemical actinometer. This compound undergoes a clean and efficient E/Z isomerization, approaching total conversion upon irradiation at 365 nm. Thanks to its properties, it can be used to determine the photon flux in the UV-visible region, with simple experimental methods and data treatment, and with the possibility to be reused after photochemical or thermal reset.

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.

Triazonine-based bistable photoswitches: synthesis, characterization and photochromic properties.

We disclose here dibenzotriazonines as a new class of nine-membered cyclic azobenzenes displaying a nitrogen function in the saturated ring chain. The specific features of these compounds are (i) a preferred E-configuration, (ii) high bi-directional photoswitching and (iii) good thermal stability of both E- and Z-forms.

A Photo- and Redox-Driven Two-Directional Terthiazole-Based Switch: A Combined Experimental and Computational Investigation.

Terthiazoles with redox-active substituents like an N-methyl pyridinium group and ferrocene have been synthesized and their photo- and electro-chromic behaviors were investigated. The presence of two lateral N-methyl pyridinium substituents in the structure of terthiazole proved to be effective in inducing not only the reductive ring-closure of the terthiazole core but also its oxidative ring-opening reaction, leading to the first terarylene-based switch able to fully operate both photochemically and electrochemically. Moreover, the large increase in the redox potential between its open and closed form (700 mV) means that a part of the photon energy necessary to trigger the cyclization is stored in the form of chemical potential available for other works. Introduction of a second redox-active unit such as ferrocene onto the central thiazolyl moiety is found to inhibit the photochromism of the switch but not its redox switchability, which, instead, got improved for the ring-opening reaction via the redox properties of the ferrocenyl unit. The optical and redox properties of the switch in its different oxidation states are analyzed with the aid of DFT calculations in order to rationalize different switching processes.

Synthesis and properties of photoswitchable diphosphines and gold(I) complexes derived from azobenzenes.

Diphosphines displaying azobenzene scaffolds and the corresponding bis-gold chloride complexes have been prepared and fully characterized by photophysical, spectroscopic and X-ray diffraction studies. DFT calculations provide complementary information on their electronic, structural and spectroscopic properties. Comparative investigations have been carried out on compounds featuring phosphorus functions in the meta- and para-positions, respectively, with respect to the azo functions, as well as on diphosphines with an ortho-tetrafluoro substituted azobenzene core. The effects of the substitution patterns on structural and spectroscopic properties are discussed.

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.

Mechanical Modulation of the Solid-State Luminescence of Tricarbonyl Rhenium(I) Complexes through the Interplay between Two Triplet Excited States.

Mechanoresponsive luminescence (MRL) materials promise smart devices for sensing, optoelectronics and security. We present here the first report on the MRL activity of two ReI complexes, opening up new opportunities for applications in these fields. Both complexes exhibit marked solid-state luminescence enhancement (SLE). Furthermore, the pristine microcrystalline powders emit in the yellow-green region, and grinding led to an amorphous phase with concomitant emission redshift and shrinking of the photoluminescence (PL) quantum yields and lifetimes. Quantum chemical calculations revealed the existence of two low-lying triplet excited states with very similar energy levels, that is, 3 IL and 3 MLCT, having, respectively, almost pure intraligand (IL) and metal-to-ligand charge-transfer (MLCT) character. Transition between these states could be promoted by rotation around the pyridyltriazole-phenylbenzoxazole bond. In the microcrystals, in which rotations are hindered, the 3 IL state induces the prominent PL emission at short wavelengths. Upon grinding, rotation is facilitated and the transition to the 3 MLCT state results in a larger proportion of long-wavelength PL. FTIR and variable-temperature PL spectroscopy showed that the opening of the vibrational modes favours non-radiative deactivation of the triplet states in the amorphous phase. In solution, PL only arises from the 3 MLCT state. The same mechanism accounts for the spectroscopic differences observed when passing from crystals to amorphous powders, and then to solutions, thereby clarifying the link between SLE and MRL for these complexes.

Photophysical Properties of 4-Dicyanomethylene-2-methyl-6-(p-dimethylamino-styryl)-4H-pyran Revisited: Fluorescence versus Photoisomerization.

Invited for the cover of this issue are Juan Xie, Rémi Métivier and co-workers at Université Paris-Saclay and Università di Bologna. The image depicts the fluorescence of the DCM molecule reported in this manuscript. Read the full text of the article at 10.1002/chem.202002828.