From single molecule to molecular aggregation science

As a type of room temperature phosphorescence (RTP) material, carbon dots (CDs) always show short lifetime and low phosphorescence efficiency. To counter these disadvantages, several strategies, such as embedding in rigid matrix, introducing of heteroatom, crosslink-enhanced emission, etc., are well developed. Consequently, lots of CDs-based RTP materials are obtained. Doping of CDs into various matrix is the dominant method for preparation of long-lived CDs-based RTP materials so far. The desired CDs@matrix composites always display outstanding RTP performances. Meanwhile, matrix-free CDs and carbonized polymer dots-based RTP materials are also widely developed. Amounts of CDs possessing ultra-long lived, multiple colored, and dynamic RTP emission are successfully obtained. Herein, the recent progress achieved in CDs-based RTP materials as well as the corresponding efficient strategies and emission mechanisms are summarized and reviewed in detail. Due to CDs-based RTP materials possess excellent chemical stability, photostability and low biological toxicity, they exhibit great application potential in the fields of anti-counterfeiting, data encryption, and biological monitoring. The application of the CDs-based RTP materials is also introduced in this review. As a promising functional material, development of long wavelength RTP emitting CDs with long lifetime is still challengeable, especially for the red and near-infrared emitting RTP materials.

Long-Lived Dynamic Room Temperature Phosphorescence from Carbon Dots Based Materials.

The search for color‐tunable, efficient, and robust scintillators plays a vital role in the development of modern X‐ray radiography. The radioluminescence tuning of copper iodide cluster scintillators in the entire visible region by bandgap engineering is herein reported. The bandgap engineering benefits from the fact that the conduction band minimum and valence band maximum of copper iodide cluster crystals are contributed by atomic orbitals from the inorganic core and organic ligand components, respectively. In addition to high scintillation performance, the as‐prepared crystalline copper iodide cluster solids exhibit remarkable resistance toward both moisture and X‐ray irradiation. These features allow copper iodide cluster scintillators to show particular attractiveness for low‐dose X‐ray radiography with a detection limit of 55  nGy s−1, a value ≈100 times lower than a standard dosage for X‐ray examinations. The results suggest that optimizing both inorganic core and organic ligand for the building blocks of metal halide cluster crystals may provide new opportunities for a new generation of high‐performance scintillation materials.

https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/advs.202205526

Color‐Tunable and Stable Copper Iodide Cluster Scintillators for Efficient X‐Ray Imaging

ConspectusX-ray luminescence is an optical phenomenon in which chemical compounds known as scintillators can emit short-wavelength light upon the excitation of X-ray photons. Since X-rays exhibit well-recognized advantages of deep penetration toward tissues and a minimal autofluorescence background in biological samples, X-ray luminescence has been increasingly becoming a promising optical tool for tackling the challenges in the fields of imaging, biosensing, and theragnostics. In recent years, the emergence of nanocrystal scintillators have further expanded the application scenarios of X-ray luminescence, such as high-resolution X-ray imaging, autofluorescence-free detection of biomarkers, and noninvasive phototherapy in deep tissues. Meanwhile, X-ray luminescence holds great promise in breaking the depth dependency of deep-seated lesion treatment and achieving synergistic radiotherapy with phototherapy.In this Account, we provide an overview of recent advances in developing advanced X-ray luminescence for applications in imaging, biosensing, theragnostics, and optogenetics neuromodulation. We first introduce solution-processed lead halide all-inorganic perovskite nanocrystal scintillators that are able to convert X-ray photons to multicolor X-ray luminescence. We have developed a perovskite nanoscintillator-based X-ray detector for high-resolution X-ray imaging of the internal structure of electronic circuits and biological samples. We further advanced the development of flexible X-ray luminescence imaging using solution-processable lanthanide-doped nanoscintillators featuring long-lived X-ray luminescence to image three-dimensional irregularly shaped objects. We also outline the general principles of high-contrast in vivo X-ray luminescence imaging which combines nanoscintillators with functional biomolecules such as aptamers, peptides, and antibodies. High-quality X-ray luminescence nanoprobes were engineered to achieve the high-sensitivity detection of various biomarkers, which enabled the avoidance of interference from the biological matrix autofluorescence and photon scattering. By marrying X-ray luminescence probes with stimuli-responsive materials, multifunctional theragnostic nanosystems were constructed for on-demand synergistic gas radiotherapy with excellent therapeutic effects. By taking advantage of the capability of X-rays to penetrate the skull, we also demonstrated the development of controllable, wireless optogenetic neuromodulation using X-ray luminescence probes while obviating damage from traditional optical fibers. Furthermore, we discussed in detail some challenges and future development of X-ray luminescence in terms of scintillator synthesis and surface modification, mechanism studies, and their other potential applications to provide useful guidance for further advancing the development of X-ray luminescence.

Advancing X-ray Luminescence for Imaging, Biosensing, and Theragnostics.

Room-temperature phosphorescence (RTP) has gained much attention in organic light-emitting diodes (OLEDs), anti-counterfeiting, encryption and bioimaging. However, efficient RTP is typically difficult due to the spin-forbidden transition nature and susceptibility to environment quenching. In aqueous phase, such quenching is much more pronounced, leading to the collection of aqueous RTP even more challenging. Assembly systems (either organic or inorganic), provide an excellent microenvironment for accommodating of phosphors in aqueous phase, due to the excluding of typical phosphorescence quenchers (H2O and O2) and rigidification of phosphorescent molecules for inhibition of non-radiative transitions (molecular motions). Herein, we summarized the recent progress in harvesting RTP from aqueous systems via various assembling strategies, including small molecules, supramolecular inclusion, and inorganic assembly. More specifically, the analytical explorations of these systems were discussed, from the perspective of the relationship between analytes and phosphorescence. Last, the further developments of aqueous RTP analysis were also prospected. 

Aqueous Room‐Temperature Phosphorescence from Assembled Phosphors for Analytical Detection

Abstract Scintillators that exhibit X-ray-excited luminescence have great potential in radiation detection, X-ray imaging, radiotherapy, and non-destructive testing. However, most reported scintillators are limited to inorganic or organic crystal materials, which have some obstacles in repeatability and processability. Here we present a facile strategy to achieve the X-ray-excited organic phosphorescent scintillation from amorphous copolymers through the copolymerization of the bromine-substituted chromophores and acrylic acid. These polymeric scintillators exhibit efficient X-ray responsibility and decent phosphorescent quantum yield up to 51.4% under ambient conditions. The universality of the design principle was further confirmed by a series of copolymers with multi-color radioluminescence ranging from green to orange-red. Moreover, we demonstrated their potential application in X-ray radiography. This finding not only outlines a feasible principle to develop X-ray responsive phosphorescent polymers, but also expands the potential applications of polymer materials with phosphorescence features. 

/pdf/organic-phosphorescent-scintillation-from-copolymers-by-x-2jxyvb3h.pdf

Organic phosphorescent scintillation from copolymers by X-ray irradiation

Abstract Intermolecular interactions, including attractive and repulsive interactions, play a vital role in manipulating functionalization of the materials from micro to macro dimensions. Despite great success in generation of ultralong organic phosphorescence (UOP) by suppressing non-radiative transitions through attractive interactions recently, there is still no consideration of repulsive interactions on UOP. Herein, we proposed a feasible approach by introducing carboxyl groups into organic phosphors, enabling formation of the intense repulsive interactions between the isolated molecules and the matrix in rigid environment. Our experimental results show a phosphor with a record lifetime and quantum efficiency up to 3.16 s and 50.0% simultaneously in film under ambient conditions. Considering the multiple functions of the flexible films, the potential applications in anti-counterfeiting, afterglow display and visual frequency indicators were demonstrated. This finding not only outlines a fundamental principle to achieve bright organic phosphorescence in film, but also expands the potential applications of UOP materials. 

/pdf/ultralong-organic-phosphorescence-from-isolated-molecules-23duqa84.pdf

Ultralong organic phosphorescence from isolated molecules with repulsive interactions for multifunctional applications

Abstract Purely organic phosphorescent materials with dynamically tunable optical properties and persistent luminescent characteristics enable more novel applications in intelligent optoelectronics. Herein, we reported a concise and universal strategy to achieve photoactivated ultralong phosphorescence at room temperature through stereo-hindrance engineering. Such dynamically photoactivated phosphorescence behavior was ascribed to the suppression of non-radiative transitions and improvement of spin-orbit coupling (SOC) as the variation of the distorted molecular conformation by the synergistic effect of electrostatic repulsion and steric hindrance. This “trainable” phosphorescent behavior was first proposed to mimic biological synaptic plasticity, especially for unique experience-dependent plasticity, by the manipulation of pulse intensity and numbers. This study not only outlines a principle to design newly dynamic phosphorescent materials, but also broadens their utility in intelligent sensors and robotics. 

/pdf/photoactivated-organic-phosphorescence-by-stereo-hindrance-2x8of747.pdf

Photoactivated organic phosphorescence by stereo-hindrance engineering for mimicking synaptic plasticity

Achieving multicolor organic afterglow materials with narrowband emission and high color purity is important in various optoelectronic fields but remains a great challenge. Here, we present an efficient strategy to obtain narrowband organic afterglow materials via Förster resonance energy transfer from long-lived phosphorescence donors to narrowband fluorescence acceptors in a polyvinyl alcohol matrix. The resulting materials exhibit narrowband emission with full width at half maximum (FWHM) as small as 23 nm and the longest lifetime of 721.22 ms. Meanwhile, by pairing the appropriate donors and acceptors, multicolor and high color purity afterglow ranging from green to red with the maximum photoluminescence quantum yield of 67.1% are achieved. Moreover, given their long luminescence lifetime, high color purity, and flexibility, we demonstrate the potential applications in high-resolution afterglow displays and dynamic and quick information identification in low-light conditions. This work provides a facile approach for developing multicolor and narrowband afterglow materials as well as expands the features of organic afterglow. This article is protected by copyright. All rights reserved.

Yuanyuan Zhang

Papers

Organic phosphorescent scintillation from copolymers by X-ray irradiation

Ultralong organic phosphorescence from isolated molecules with repulsive interactions for multifunctional applications

Photoactivated organic phosphorescence by stereo-hindrance engineering for mimicking synaptic plasticity

Narrowband Organic Afterglow via Phosphorescence Förster Resonance Energy Transfer for Multifunctional Applications.