Correction: Water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles enabling a humidity-responsive luminescence color change.

Correction for 'Water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles enabling a humidity-responsive luminescence color change' by Tomoya Enjou , , 2024, https://doi.org/10.1039/d3cc05749f.

Tetracene cyclophanes showing controlled intramolecular singlet fission by through-space orientations.

Tetracene cyclophanes: a series of cyclic tetracene dimers bridged by two flexible ethylene glycol units demonstrated enhanced intramolecular singlet fission through through-space orientations by suppressing the H-type excited complex.

Water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles enabling a humidity-responsive luminescence color change.

Novel water-dispersible donor-acceptor-donor π-conjugated bolaamphiphiles, having dibenzophenazine as the acceptor and heteroatom-bridged amphiphilic diarylamines as the donors, have been developed. The materials displayed a distinct photoluminescence color change in response to humidity in a poly(vinylalcohol) matrix.

Enhanced Photothermal Property of NDI-Based Conjugated Polymers by Copolymerization with a Thiadiazolobenzotriazole Unit.

Solar steam generation (SSG) is a promising photothermal technology to solve the global water storage issue. The potential of π-conjugated polymers as photothermal materials is significant, because their absorption range can be customized through molecular design. In this study, naphthalenediimide (NDI) and thiadiazolobenzotriazole (TBZ) were employed as bifunctional monomers to produce conjugated polymers.

Microscopic strain mapping in polymers equipped with non-covalent mechanochromic motifs.

The mechanical failure of polymers remains challenging to understand and predict, as it often involves highly localised phenomena that cannot be probed with bulk characterisation techniques. Here, we present a generalisable protocol based on optical microscopy, tensile testing, and image processing that permits the spatially resolved interrogation of mechanical deformation at the molecular level around defects in mechanophore-containing polymers. The approach can be applied to a broad range of polymeric materials, mechanophores, and deformation scenarios.

Force-Induced Shuttling of Rotaxanes Controls Fluorescence Resonance Energy Transfer in Polymer Hydrogels.

The molecular shuttling function of rotaxanes can be exploited to design mechanoresponsive reporter molecules. Here, we report a new approach to such rotaxane-based mechanophores, in which the fluorescence resonance energy transfer (FRET) between a donor-acceptor pair is mechanically controlled. A cyclic molecule containing a green-light-emitting FRET donor connected to a red-light-emitting FRET acceptor was threaded onto an axle equipped with a quencher at its center and two stoppers in the peripheral positions.

Excited State Charge-Transfer Complexes Enable Fluorescence Color Changes in a Supramolecular Cyclophane Mechanophore.

Mechanochromic mechanophores are reporter molecules that indicate mechanical events through changes of their photophysical properties. Supramolecular mechanophores in which the activation is based on the rearrangement of luminophores and/or quenchers without any covalent bond scission, remain less well investigated. Here, we report a cyclophane-based supramolecular mechanophore that contains a 1,6-bis(phenylethynyl)pyrene luminophore and a pyromellitic diimide quencher.

Supramolecular Rings as Building Blocks for Stimuli-Responsive Materials.

Stimuli-responsive polymers are of great interest due to their ability to translate changing environmental conditions into responses in defined materials. One possibility to impart such behavior is the incorporation of optically active molecules into a polymer host. Here, we describe how sensor molecules that consist of a π-extended benzothiadiazole emitter and a naphthalene diimide quencher can be exploited in this context.

Rotaxane-Based Dual Function Mechanophores Exhibiting Reversible and Irreversible Responses.

Mechanochromic mechanophores permit the design of polymers that indicate mechanical events through optical signals. Here we report rotaxane-based supramolecular mechanophores that display both reversible and irreversible fluorescence changes. These responses are triggered by different forces and are achieved by exploiting the molecular shuttling function and force-induced dethreading of rotaxanes.

Folded Perylene Diimide Loops as Mechanoresponsive Motifs.

A supramolecular mechanophore that can be integrated into polymers and indicates deformation by a fluorescence color change is reported. Two perylene diimides (PDIs) were connected by a short spacer and equipped with peripheral atom transfer polymerization initiators. In the idle state, the motif folds into a loop and its emission is excimer dominated.

Mechanically Responsive Luminescent Polymers Based on Supramolecular Cyclophane Mechanophores.

A new approach to cyclophane-based supramolecular mechanophores is presented. We report a mechanically responsive cyclic motif that contains two fluorescent 1,6-bis(phenylethynyl)pyrene moieties that are capable of forming intramolecular excimers. The emission spectra of dilute solutions of this cyclophane and a polyurethane elastomer into which a small amount of the mechanophore (0.

Mechanochromic Luminescence from Crystals Consisting of Intermolecular Hydrogen-Bonded Sheets.

Introduction of functional groups that can form intermolecular hydrogen bonds into highly-emissive luminophores is a promising way to induce mechanochromic luminescence. Herein, we report that a 9,10-bis(phenylethynyl)anthracene derivative featuring two amide groups forms green-emissive crystals based on two-dimensional hydrogen-bonded molecular sheets. Mechanical grinding changed the emission from green to yellow, owing to a transition from a crystalline to an amorphous phase.

Temperature-Controlled Locally Excited and Twisted Intramolecular Charge-Transfer State-Dependent Fluorescence Switching in Triphenylamine-Benzothiazole Derivatives.

Triphenylamine-benzothiazole derivatives, -(4-(benzo[]thiazol-2-yl)phenyl)--phenylbenzenamine (), -(4-(benzo[]thiazol-2-yl)-3-methoxyphenyl)--phenylbenzenamine (), and 2-(benzo[]thiazol-2-yl)-5-(diphenylamino)phenol (), showed unusual temperature-controlled locally excited (LE) and twisted intramolecular charge-transfer (TICT) state fluorescence switching in polar solvents. The detailed photophysical studies (absorption, fluorescence, lifetime, and quantum yield) in various solvents confirmed polarity-dependent LE and TICT state formation and fluorescence tuning. and exhibited strong fluorescence with short lifetime in nonpolar solvents compared to polar solvents.

Mechanoresponsive Behavior of a Polymer-Embedded Red-Light Emitting Rotaxane Mechanophore.

A red light-emitting photoluminescent supramolecular mechanophore based on an interlocked molecular motif is presented. The rotaxane-based mechanophore contains a cyclic compound featuring a π-extended 4,4-difluoro-4-bora-3a,4a-diaza--indacene (BODIPY) dye as a red emitter that was threaded onto a dumbbell-shaped molecule containing an electron-poor 1,4,5,8-naphthalenetetracarboxylic diimide quencher at its center. Through two aliphatic hydroxyl groups attached to the dumbbell and the cycle, the mechanophore was covalently embedded into the backbone of a thermoplastic polyurethane elastomer.

Rotaxane-Based Mechanophores Enable Polymers with Mechanically Switchable White Photoluminescence.

Three mechanoresponsive polyurethane elastomers whose blue, green, and orange photoluminescence can be reversibly turned on by mechanical force were prepared and combined to create a blend that exhibits deformation-induced white photoluminescence. The three polyurethanes contain rotaxane-based supramolecular mechanoluminophores based on π-extended pyrene, anthracene, or 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4-pyran (DCM) luminophores, respectively, and 1,4,5,8-naphthalenetetracarboxylic diimide as an electronically matched quencher. Each polymer shows instantly reversible, strain-dependent switching of its photoluminescence intensity when stretched and relaxed, as deformation leads to a spatial separation of the luminophore and quencher.

Mechano- and Photoresponsive Behavior of a Bis(cyanostyryl)benzene Fluorophore.

The mechanoresponsive behavior and photochemical response of a new bis(cyanostyryl)benzene fluorophore (CSB-5) were investigated. Green fluorescence with λ of 507 nm was found for CSB-5 in chloroform solution, mirroring the behavior of a previously reported similar dye (CSB-6). Alternatively, crystalline samples of CSB-5 exhibited orange fluorescence with λ of 620 nm, attributable to excimer emission.

Functional Polymers Through Mechanochemistry.

While coupling mechanical and chemical processes is widespread in living organisms, the idea to harness the mechanically induced dissociation of weak covalent and non-covalent bonds to create artificial materials that respond to mechanical stimulation has only recently gained attention. Here we summarize our activities that mainly revolve around the exploitation of non-covalent interactions in (supramolecular) polymeric materials with the goal to translate mechanical stresses into useful, pre-defined events. Focusing on mechano- chromic polymers that alter their optical absorption or fluorescence properties, several new operating principles, mechanosensitive entities, and materials systems were developed.

Mechanoresponsive, Luminescent Polymer Blends Based on an Excimer-Forming Telechelic Macromolecule.

A well-known approach toward mechanochromic polymers relies on the incorporation of excimer-forming fluorophores into a matrix polymer and the disruption of aggregated chromophores when such materials undergo macroscopic mechanical deformation. However, the required aggregates and stress-transfer processes have so far only been realized with select dye/polymer combinations. As demonstrated here, the utility of this approach can be extended by tethering an excimer-forming cyano-substituted oligo(p-phenylene vinylene) fluorophore to the two ends of a telechelic poly(ethylene-co-butylene) and blending small amounts (0.

Unusual fluorescent photoswitching of imidazole derivatives: the role of molecular conformation and twist angle controlled organic solid state fluorescence.

Molecular photoswitching, light induced reversible color/fluorescence modulation, has mostly been realized in organic molecules via E/Z isomerization of azobenzenes and stilbenes and ring opening/closing reactions of spiropyrans and diarylethenes. We report here new fluorescent molecular photoswitches based on triphenylamine (TPA)-imidazole derivatives, N-phenyl-N-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)benzenamine (NTPB) and N-phenyl-N-(4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)benzenamine (NPPB), that exhibited light induced reversible fluorescence switching via conformational change from a twisted molecular structure to more planar. NTPB and NPPB in CHCl3 showed red shift of absorption and fluorescence upon UV light irradiation whereas white light exposure reversed both absorption as well as fluorescence.

Stimuli-Responsive Dual-Color Photon Upconversion: A Singlet-to-Triplet Absorption Sensitizer in a Soft Luminescent Cyclophane.

Reversible emission color switching of triplet-triplet annihilation-based photon upconversion (TTA-UC) is achieved by employing an Os complex sensitizer with singlet-to-triplet (S-T) absorption and an asymmetric luminescent cyclophane with switchable emission characteristics. The cyclophane contains the 9,10-bis(phenylethynyl)anthracene unit as an emitter and can assemble into two different structures, a stable crystalline phase and a metastable supercooled nematic phase. The two structures exhibit green and yellow fluorescence, respectively, and can be accessed by distinct heating/cooling sequences.

Rotaxanes as Mechanochromic Fluorescent Force Transducers in Polymers.

The integration of mechanophores, motifs that transduce mechanical forces into chemical reactions, allows creating materials with stress-dependent properties. Typical mechanophores are activated by cleaving weak covalent bonds, but these reactions can also be triggered by other stimuli, and this renders the behavior unspecific. Here we show that this problem can be overcome by extending the molecular-shuttle function of rotaxanes to mechanical activation.

Mechano- and Thermoresponsive Photoluminescent Supramolecular Polymer.

Mechanoresponsive luminescent (MRL) materials change their emission color upon application of external forces. Many dyes with MRL behavior are known, but they normally do not display useful mechanical properties. Here, we introduce a new approach to overcome this problem, which relies on combining MRL compounds with the concept of supramolecular polymerization.

A mechano- and thermoresponsive luminescent cyclophane.

The first fluorescent cyclophane with mechano- and thermoresponsive solid-state fluorescence characteristics is reported. The new cyclophane comprises two 9,10-bis(phenylethynyl)anthracene moieties that are bridged by tetraethylene glycol spacers. The stimuli-responsiveness is based on molecular assembly changes.

A Thermo- and Mechanoresponsive Cyano-Substituted Oligo(p-phenylene vinylene) Derivative with Five Emissive States.

Multiresponsive materials that display predefined photoluminescence color changes upon exposure to different stimuli are attractive candidates for advanced sensing schemes. Herein, we report a cyano-substituted oligo(p-phenylene vinylene) (cyano-OPV) derivative that forms five different solvent-free solid-state molecular assemblies, luminescence properties of which change upon thermal and mechanical stimulation. Single-crystal X-ray structural analysis suggested that tolyl groups introduced at the termini of solubilizing side-chains of the cyano-OPV play a pivotal role in its solid-state arrangement.