Multivalent supramolecular assembly with ultralong organic room temperature phosphorescence,high transfer efficiency and ultrahigh antenna effect in water

Multivalent supramolecular assemblies have recently attracted extensive attention in the applications of soft materials and cell imaging. Here, we report a novel multivalent supramolecular assembly constructed from 4-(4-bromophenyl)pyridine-1-ium bromide modified hyaluronic acid (HABr), cucurbit[8]uril (CB[8]) and laponite® clay (LP), which could emit purely organic room-temperature phosphorescence (RTP) with a phosphorescence lifetime of up to 4.79 ms in aqueous solution via multivalent supramolecular interactions. By doping the organic dyes rhodamine B (RhB) or sulfonated rhodamine 101 (SR101) into the HABr/CB[8]/LP assembly, phosphorescence energy transfer was realized with high transfer efficiency (energy transfer efficiency = 73–80%) and ultrahigh antenna effect (antenna effect value = 308–362) within the phosphorescent light harvesting system. Moreover, owing to the dynamic nature of the noncovalent interactions, a wide-range spectrum of phosphorescence energy transfer outputs could be obtained not only in water but also on filter paper and a glass plate by adjusting the donor–acceptor ratio and, importantly, white-light emission was obtained, which could be used in the application of information encryption.

An ultralong lifetime supramolecular assembly was constructed via multivalent supramolecular interactions and achieved phosphorescence light harvesting. Multicolor (including white) broad-spectrum outputs could be achieved in water and also on filter paper and a glass plate.     

Photo-induced ultralong phosphorescence of carbon dots for thermally sensitive dynamic patterning

Stimuli-responsive films with a dynamic long afterglow feature have received considerable attention in the field of optical materials. Herein, we report the unique dynamic ultralong room temperature phosphorescence (URTP) in flexible solid films made of luminescent carbon dots (CDs) and polyvinylpyrrolidone (PVP). Impressively, fully reversible photo-activation and thermal deactivation of the dynamic long afterglow was achieved in this material, with a lifetime on–off ratio exceeding 3900. Subsequently, ultra-fine URTP patterns (resolution > 1280 dpi) with thermally sensitive retention time were readily photo-printed onto the films and utilized as time–temperature indicating logistics labels with multi-editing capacity. These findings not only enrich the library of dynamic URTP materials, but also extend the scope of the potential applications of luminescent CDs.

A flexible CD–polymer composite with a reversibly editable photo-induced URTP long afterglow was rationally designed and successfully applied in dynamic optical patterning with built-in time–temperature indicating functionality.     

A metal-free 2D layered organic ammonium halide framework realizing full-color persistent room-temperature phosphorescence

Organic–inorganic hybrid metal halides have attracted intensive attention because of their unique electronic structure and solution processability. They have a rigid micro/nano-structure and heavy atom effect, which has obvious advantages in promoting organic room temperature phosphorescence (RTP). However, the toxicity of heavy metals has limited their further development. Herein, two metal-free 2D layered ammonium halides, homopiperonylammonium bromide and chloride (HLB and HLC), are described for the first time. Their layered structure consists of rigid inorganic ammonium halide laminates and neatly stacked organic layers. The rigid laminates and external heavy atom effect of halogen atoms make HLB and HLC produce green RTP. When phosphor guests with different triplet energies are doped into HLB, HLC, or phenylethylamine salt hosts, effective full-color and even white ultra-long RTP with phosphorescence quantum yield up to 18.7% and lifetime up to 1.7 s is realized through energy transfer between the host and guest. Due to the simple solution synthesis, 10 g-level doped layered organic ammonium halides with the same phosphorescence properties can be easily obtained. The information ink based on these doped halides and non-toxic ethanol solvent can form various patterns on filter paper. The fluorescence and phosphorescence of these patterns are sensitive to the excitation wavelength and acid–base vapor. Consequently, they can be applied to multiple complex anti-counterfeiting and fluorescence/phosphorescence dual-mode chemical sensors.

A kind of metal-free organic ammonium halides characterized by a unique 2D layered structure show colorful ultralong phosphorescence. Phosphorescent quantum yield (up to 19%) and lifetime (up to 1.7 s) can be tuned by doping with different phosphors.     

Converting molecular luminescence to ultralong room-temperature phosphorescence via the excited state modulation of sulfone-containing heteroaromatics

Manipulating the molecular orbital properties of excited states and the subsequent relaxation processes can greatly alter the emission behaviors of luminophores. Herein we report a vivid example of this, with luminescence conversion from thermally activated delayed fluorescence (TADF) to ultralong room-temperature phosphorescence (URTP) via a facile substituent effect on a rigid benzothiazino phenothiazine tetraoxide (BTPO) core. Pristine BTPO with multiple heteroatoms shows obvious intramolecular charge transfer (ICT) excited states with small exchange energy, featuring TADF. Via delicately functionalizing the BTPO core with peripheral moieties, the excited states of the BTPO derivatives become a hybridized local and charge transfer (HLCT) state in the S₁ state and a local excitation (LE) dominated HLCT state in the T₁ state, with enlarged energy bandgaps. Upon dispersion in a polymer matrix, the BTPO derivatives exhibit a persistent bright green afterglow with long lifetimes of up to 822 ms and decent quantum yields of up to 11.6%.

The decoration of a BTPO core results in a change in the luminescence nature from TADF to URTP. The phosphors in an amorphous PMMA matrix showed monomeric URTP with phosphorescence lifetimes of up to 822 ms and quantum yields of up to 11.6%.     

Direct photo-induced reductive Heck cyclization of indoles for the efficient preparation of polycyclic indolinyl compounds

The photo-induced cleavage of C(sp²)–Cl bonds is an appealing synthetic tool in organic synthesis, but usually requires the use of high UV light, photocatalysts and/or photosensitizers. Herein is described a direct photo-induced chloroarene activation with UVA/blue LEDs that can be used in the reductive Heck cyclization of indoles and without the use of a photocatalyst or photosensitizer. The indole compounds examined display room-temperature phosphorescence. The photochemical reaction tolerates a panel of functional groups including esters, alcohols, amides, cyano and alkenes (27 examples, 50–88% yields), and can be used to prepare polycyclic compounds and perform the functionalization of natural product analogues in moderate to good yields. Mechanistic experiments, including time-resolved absorption spectroscopy, are supportive of photo-induced electron transfer between the indole substrate and DIPEA, with the formation of radical intermediates in the photo-induced dearomatization reaction.

Metal- and photocatalyst-free reductive Heck cyclization of indoles under light irradiation was developed and used to prepare polycyclic compounds and functionalize natural product analogues in moderate to good yields.     

Self-trapped exciton emission and piezochromism in conventional 3D lead bromide perovskite nanocrystals under high pressure

Developing single-component materials with bright-white emission is required for energy-saving applications. Self-trapped exciton (STE) emission is regarded as a robust way to generate intrinsic white light in halide perovskites. However, STE emission usually occurs in low-dimensional perovskites whereby a lower level of structural connectivity reduces the conductivity. Enabling conventional three-dimensional (3D) perovskites to produce STEs to elicit competitive white emission is challenging. Here, we first achieved STEs-related emission of white light with outstanding chromaticity coordinates of (0.330, 0.325) in typical 3D perovskites, Mn-doped CsPbBr₃ nanocrystals (NCs), through pressure processing. Remarkable piezochromism from red to blue was also realized in compressed Mn-doped CsPbBr₃ NCs. Doping engineering by size-mismatched Mn dopants could give rise to the formation of localized carriers. Hence, high pressure could further induce octahedra distortion to accommodate the STEs, which has never occurred in pure 3D perovskites. Our study not only offers deep insights into the photophysical nature of perovskites, it also provides a promising strategy towards high-quality, stable white-light emission.

We first achieved self-trapped exciton emission with outstanding white-light chromaticity coordinates of (0.330, 0.325) in conventional 3D halide perovskite nanocrystals through pressure engineering.     

Narrowband blue emission with insensitivity to the doping concentration from an oxygen-bridged triarylboron-based TADF emitter: nondoped OLEDs with a high external quantum efficiency up to 21.4%

Blue thermally activated delayed fluorescence (TADF) emitters that can simultaneously achieve narrowband emission and high efficiency in nondoped organic light-emitting diodes (OLEDs) remain a big challenge. Herein, we successfully design and synthesize two blue TADF emitters by directly incorporating carbazole fragments into an oxygen-bridged triarylboron acceptor. Depending on the linking mode, the two emitters show significantly different photophysical properties. Benefitting from the bulky steric hindrance between the acceptor and terminal pendants, the blue emitter TDBA-Cz exhibited a high photoluminescence quantum yield (PLQY) of 88% in neat films and narrowband emission. The corresponding non-doped blue device exhibited a maximum external quantum efficiency (EQE) of 21.4%, with a full width at half maximum (FWHM) of only 45 nm. This compound is the first blue TADF emitter that can concurrently achieve narrow bandwidth and high electroluminescence (EL) efficiency in nondoped blue TADF-OLEDs.

A donor–acceptor TADF emitter showed narrowband high-efficiency blue emission by fine molecular modulation. The corresponding OLEDs exhibited a maximum EQE of 21.4% and a small FWHM of 45 nm, representing the most efficient nondoped blue TADF-OLEDs.     

The switchable phosphorescence and delayed fluorescence of a new rhodamine-like dye through allenylidene formation in a cyclometallated platinum(ii) system

A new rhodamine-like alkyne-substituted ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. The chemo-induced “ON–OFF” switching capabilities on the spirolactone ring of the Rhodyne ligand with an end-capping platinum(ii) metal centre can modulate the interesting acetylide–allenylidene resonance. The long-lived ³IL excited state of Rhodyne in its ON state as an optically active opened form was revealed via steady-state and time-resolved spectroscopy studies. Exceptional near-infrared (NIR) phosphorescence and delayed fluorescence based on a rhodamine-like structure were observed at room temperature for the first time. The position of the alkyne communication bridge attached to the platinum(ii) unit was found to vary the lead(ii)-ion binding mode and also the possible resonance structure for metal-mediated allenylidene formation. The formation of a proposed allenylidene resonance structure was suggested to rationalize these phenomena.

A new rhodamine-like ligand (Rhodyne) was designed to coordinate a cyclometallated platinum(ii) system. Allenylidene formation could trigger NIR phosphorescence at 740 nm originating from Rhodyne ³IL, as well as delayed fluorescence at 620 nm.     

(Fluoro)alkylation of alkenes promoted by photolysis of alkylzirconocenes

Difluoroalkylated compounds have important applications in pharmaceutical, agrochemical, and materials science. However, efficient methods to construct the alkylCF₂–alkyl bond are very limited, and the site-selective introduction of a difluoromethylene (CF₂) group into an aliphatic chain at the desired position remains challenging. Here, we report an unprecedented example of alkylzirconocene promoted difluoroalkylation of alkyl- and silyl-alkenes with a variety of unactivated difluoroalkyl iodides and bromides under the irradiation of visible light without a catalyst. The resulting difluoroalkylated compounds can serve as versatile synthons in organic synthesis. The reaction can also be applied to activated difluoroalkyl, trifluoromethyl, perfluoroalkyl, monofluoroalkyl, and nonfluorinated alkyl halides, providing a general method to controllably access fluorinated compounds. Preliminary mechanistic studies reveal that a single electron transfer (SET) pathway induced by a Zr(iii) species is involved in the reaction, in which the Zr(iii) species is generated by the photolysis of alkylzirconocene with blue light.

An unprecedented example of alkylzirconocene promoted difluoroalkylation of alkyl- and silyl-alkenes with a variety of fluoroalkyl and nonfluoroalkyl halides under the irradiation of visible light has been reported.     

Targeted protein oxidation using a chromophore-modified rapamycin analog

Chemically induced dimerization of FKBP and FRB using rapamycin and rapamycin analogs has been utilized in a variety of biological applications. Formation of the FKBP-rapamycin-FRB ternary complex is typically used to activate a biological process and this interaction has proven to be essentially irreversible. In many cases, it would be beneficial to also have temporal control over deactivating a biological process once it has been initiated. Thus, we developed the first reactive oxygen species-generating rapamycin analog toward this goal. The BODIPY-rapamycin analog BORap is capable of dimerizing FKBP and FRB to form a ternary complex, and upon irradiation with 530 nm light, generates singlet oxygen to oxidize and inactivate proteins of interest fused to FKBP/FRB.

Utilization of a ROS-generating chromophore for the development of reversible control of rapamycin-induced protein dimerization via targeted oxidation.     

Electrostatic regulation of blue copper sites

In the last 50 years, the blue copper proteins became central targets of investigation. Extensive experiments focused on the Cu coordination to probe the effect of local perturbations on its properties. We found that local electric fields, generated by charged residues evolutionarily placed throughout the protein edifice, mainly second sphere, but also more remotely, constitute an additional significant factor regulating blue copper proteins. These fields are not random, but exhibit a highly specific directionality, negative with respect to the and vectors in the Cu first shell. The field magnitude contributes to fine-tuning of the geometric and electronic properties of Cu sites in individual blue copper proteins. Specifically, the local electric fields evidently control the Cu–S_Met bond distance, Cu(ii)–S_Cys bond covalency, and the energies of the frontier molecular orbitals, which, in turn, govern the Cu(ii/i) reduction potential and the relative absorption intensities at 450 nm and 600 nm.

Intramolecular electric fields in blue copper proteins are oriented in a fixed way to modulate properties of their copper sites: they control the first-shell copper interactions to influence geometric, spectroscopic, and redox behavior.     

Room-temperature phosphorescence of a supercooled liquid: kinetic stabilisation by desymmetrisation

Achieving organic room-temperature phosphorescence (RTP) in a solvent-free liquid state is a challenging task because the liquid state provides a less rigid environment than the crystal. Here, we report that an unsymmetrical heteroaromatic 1,2-diketone forms an organic RTP liquid. This diketone exists as a kinetically stable supercooled liquid, which resists crystallisation even under pricking or shearing stresses, and remains as a liquid for several months. The unsymmetrical diketone core is flexible, with eight distinct conformers possible, which prevents nucleation and growth for the liquid–solid transition. Interestingly, the thermodynamically stable crystalline solid-state was non-emissive. Thus, the RTP of the diketone was found to be liquiefaction-induced. Single-crystal X-ray structure analysis revealed that the diminished RTP of the crystal is due to insufficient intermolecular interactions and restricted access to an emissive conformer. Our work demonstrates that flexible unsymmetrical skeletons are promising motifs for bistable liquid–solid molecular systems, which are useful for the further development of stimuli-responsive materials that use phase transitions.

Metal-free, single-component, unsymmetrical 1,2-diketone exhibits liquefaction-induced room-temperature phosphorescence. Desymmetrisation provides the supercooled liquid with notable kinetic stability and phase-dependent phosphorescence properties.     

Time-resolved analysis of photoluminescence at a single wavelength for ratiometric and multiplex biosensing and bioimaging

Simultaneous analysis of luminescence signals of multiple probes can improve the accuracy and efficiency of biosensing and bioimaging. Analysis of multiple signals at different wavelengths usually suffers from spectral overlap, possible energy transfer, and difference in detection efficiency. Herein, we reported a polymeric luminescent probe, which was composed of a phenothiazine-based fluorescent compound and a phosphorescent iridium(iii) complex. Both luminophores emitted at around 600 nm but their luminescence lifetimes are 160 times different, allowing time-resolved independent analysis. As the fluorescence was enhanced in response to oxidation by hypochlorite and the phosphorescence was sensitive toward oxygen quenching, a four-dimensional relationship between luminescence intensity, fluorescence/phosphorescence ratio, hypochlorite concentration, and oxygen content was established. In cellular imaging, time-resolved photoluminescence imaging microscopy clearly showed the independent fluorescence response toward hypochlorite and phosphorescence response toward oxygen in separated time intervals. This work opens up a new idea for the development of multiplex biosensing and bioimaging.

A single-wavelength dual-emissive polymeric probe shows fluorescence enhancement toward ClO⁻ and phosphorescence quenching toward O₂, allowing simultaneously imaging cellular ClO⁻ and O₂via time-resolved photoluminescence imaging microscopy.     

Achieving a blue-excitable yellow-emitting Ca-LMOF phosphor via water induced phase transformation

Luminescent metal–organic frameworks (LMOFs) with diverse structural features and promising fluorescence-based applications have attracted wide attention in the past two decades. In this work, a LMOF with the formula [Ca₄(tcbpe-F)₂(H₂O)₃] (1, LMOF-411) has been constructed from calcium (Ca) and 1,1,2,2-tetrakis(4-(4-carboxyphenyl)phenyl)ethene (H₄tcbpe-F). Compound 1 features a three-dimensional framework with a 10-nodal net topology. Due to the relatively high hydration energy of Ca²⁺, compound 1 readily transforms into a new phase formulated as [Ca(H₂tcbpe-F)(H₂O)₂] (1′) upon exposure to water. Combining experimental characterization and theoretical calculations, we elucidated the mechanism of H₂O-induced phase transition from 1 to 1′. Notably, the water induced phase transformation can be detected visibly from the change in luminescence, which originates from the fluorescent linker. Compound 1 emits green light (λ_em = 490 nm) under UV excitation, while compound 1′ emits bright yellow light (λ_em = 550 nm) under blue excitation (450 nm). Compound 1′ represents the first Ca based LMOF yellow phosphor and its luminescence quantum yield reaches 68%. It can be coated directly onto a commercial blue light-emitting-diode (LED) chip to fabricate a white LED (WLED).

The first blue-excitable calcium-based LMOF yellow phosphor is achieved via water induced phase transformation. The compound with high luminescence quantum efficiency can be coated directly onto a commercial blue LED chip to fabricate a white LED.     

Red aqueous room-temperature phosphorescence modulated by anion–π and intermolecular electronic coupling interactions

Aqueous room temperature phosphorescence (aRTP) from purely organic materials has been intriguing but challenging. In this article, we demonstrated that the red aRTP emission of 2Br–NDI, a water-soluble 4,9-dibromonaphthalene diimide derivative as a chloride salt, could be modulated by anion–π and intermolecular electronic coupling interactions in water. Specifically, the rarely reported stabilization of anion–π interactions in water between Cl⁻ and the 2Br–NDI core was experimentally evidenced by an anion–π induced long-lived emission (λ_Anion–π) of 2Br–NDI, acting as a competitive decay pathway against the intrinsic red aRTP emission (λ_Phos) of 2Br–NDI. In the initial expectation of enhancing the aRTP of 2Br–NDI by inclusion complexation with macrocyclic cucurbit[n]urils (CB[n]s, n = 7, 8, 10), we surprisingly found that the exclusion complexation between CB[8] and 2Br–NDI unconventionally endowed the complex with the strongest and longest-lived aRTP due to the strong intermolecular electronic coupling between the nπ* orbit on the carbonyl rims of CB[8] and the ππ* orbit on 2Br–NDI in water. It is anticipated that these intriguing findings may inspire and expand the exploration of aqueous anion–π recognition and CB[n]-based aRTP materials.

The aqueous room temperature phosphorescence of 2Br–NDI is modulated by long-lived-emitting anion–π interactions and tremendously enhanced by intermolecular electronic coupling interactions with the ISC-boosting carbonyl rims of CB[8] host.     

Oxime as a general photocage for the design of visible light photo-activatable fluorophores

Photoactivatable fluorophores have been widely used for tracking molecular and cellular dynamics with subdiffraction resolution. In this work, we have prepared a series of photoactivatable probes using the oxime moiety as a new class of photolabile caging group in which the photoactivation process is mediated by a highly efficient photodeoximation reaction. Incorporation of the oxime caging group into fluorophores results in loss of fluorescence. Upon light irradiation in the presence of air, the oxime-caged fluorophores are oxidized to their carbonyl derivatives, restoring strong fluorophore fluorescence. To demonstrate the utility of these oxime-caged fluorophores, we have created probes that target different organelles for live-cell confocal imaging. We also carried out photoactivated localization microscopy (PALM) imaging under physiological conditions using low-power light activation in the absence of cytotoxic additives. Our studies show that oximes represent a new class of visible-light photocages that can be widely used for cellular imaging, sensing, and photo-controlled molecular release.

Photoactivatable fluorophores have been widely used for tracking molecular and cellular dynamics with subdiffraction resolution.     

A system for artificial light signal transduction via molecular translocation in a lipid membrane

Light signal transduction pathways are the central components of mechanisms that regulate plant development, in which photoreceptors receive light and participate in light signal transduction. Chemical systems can be designed to mimic these biological processes that have potential applications in smart sensing, drug delivery and synthetic biology. Here, we synthesized a series of simple photoresponsive molecules for use as photoreceptors in artificial light signal transduction. The hydrophobic structures of these molecules facilitate their insertion into vesicular lipid bilayers, and reversible photoisomerization initiates the reciprocating translocation of molecules in the membrane, thus activating or deactivating the hydrolysis reaction of a precatalyst in the transducer for an encapsulated substrate, resulting in a light controllable output signal. This study represents the first example of using simplified synthetic molecules to simulate light signal transduction performed by complex biomolecules.

Photoisomerization chemistry was used to simulate light signal transduction, in which the light-controlled reciprocating translocation of molecules in lipids activates or deactivates the hydrolysis reaction for an encapsulated substrate.     

Sulfur(iv)-mediated umpolung α-heterofunctionalization of 2-oxazolines

The α-umpolung of carbonyl compounds significantly expands the boundaries of traditional carbonyl chemistry. Despite various umpolung methods available today, reversing the inherent reactivity of carbonyls still remains a substantial challenge. In this article, we report the first use of sulfonium salts, in lieu of well-established hypervalent iodines, for the carbonyl umpolung event. The protocol enables the incorporation of a wide variety of heteroatom nucleophiles into the α-carbon of 2-oxazolines. The success of this investigation hinges on the following factors: (1) the use of sulfoxides, which are abundant, structurally diverse and tunable, and easily accessible, ensures the identification of a superior oxidant namely phenoxathiin sulfoxide for the umpolung reaction; (2) the “assembly/deprotonation” protocol previously developed for rearrangement reactions in our laboratory was successfully applied here for the construction of α-umpoled 2-oxazolines.

Aryl sulfonium salts serving as a new type of carbonyl umpolung reagent enable direct α-heterofunctionalization of 2-oxazolines.     

Mixed lead–tin perovskite films with >7 μs charge carrier lifetimes realized by maltol post-treatment

Mixed lead–tin (Pb–Sn) halide perovskites with optimum band gaps near 1.3 eV are promising candidates for next-generation solar cells. However, the performance of solar cells fabricated with Pb–Sn perovskites is restricted by the facile oxidation of Sn(ii) to Sn(iv), which induces self-doping. Maltol, a naturally occurring flavor enhancer and strong metal binding agent, was found to effectively suppress Sn(iv) formation and passivate defects in mixed Pb–Sn perovskite films. When used in combination with Sn(iv) scavenging, the maltol surface treatment led to high-quality perovskite films which showed enhanced photoluminescence intensities and charge carrier lifetimes in excess of 7 μs. The scavenging and surface treatments resulted in highly reproducible solar cell devices, with photoconversion efficiencies of up to 21.4% under AM1.5G illumination.

Maltol, a metal binding agent, effectively passivates defects on the surface of mixed lead–tin perovskite films. The carrier lifetimes of the resultant perovskite films are over 7 μs. The solar cell devices exhibit efficiencies of up to 21.4%.     

A rechargeable molecular solar thermal system below 0 °C

An optimal temperature is crucial for a broad range of applications, from chemical transformations, electronics, and human comfort, to energy production and our whole planet. Photochemical molecular thermal energy storage systems coupled with phase change behavior (MOST-PCMs) offer unique opportunities to capture energy and regulate temperature. Here, we demonstrate how a series of visible-light-responsive azopyrazoles couple MOST and PCMs to provide energy capture and release below 0 °C. The system is charged by blue light at −1 °C, and discharges energy in the form of heat under green light irradiation. High energy density (0.25 MJ kg⁻¹) is realized through co-harvesting visible-light energy and thermal energy from the environment through phase transitions. Coatings on glass with photo-controlled transparency are prepared as a demonstration of thermal regulation. The temperature difference between the coatings and the ice cold surroundings is up to 22.7 °C during the discharging process. This study illustrates molecular design principles that pave the way for MOST-PCMs that can store natural sunlight energy and ambient heat over a wide temperature range.

We demonstrate rationally designed arylazopyrazoles as MOST-PCM that can be circularly charged and discharged below 0 °C with visible light.