Organic-Inorganic Hybrid Glasses of Atomically Precise Nanoclusters.

Organic-inorganic atomically precise nanoclusters provide indispensable building blocks for establishing structure-property links in hybrid condensed matter. However, robust glasses of ligand-protected nanocluster solids have yet to be demonstrated. Herein, we show [Cu4I4(PR3)4] cubane nanoclusters coordinated by phosphine ligands (PR3) form robust melt-quenched glasses in air with reversible crystal-liquid-glass transitions. Protective phosphine ligands critically influence the glass formation mechanism, modulating the glasses' physical properties. A hybrid glass utilizing ethyldiphenylphosphine-based nanoclusters, [Cu4I4(PPh2Et)4], exhibits superb optical properties, including >90% transmission in both visible and near-infrared wavelengths, negligible self-absorption, near-unity quantum yield, and high light yield. Experimental and theoretical analyses demonstrate the structural integrity of the [Cu4I4(PPh2Et)4] nanocluster, i.e., iodine-bridged tetranuclear cubane, has been fully preserved in the glass state. The strong internanocluster CH-π interactions found in the [Cu4I4(PPh2Et)4] glass and subsequently reduced structural vibration account for its enhanced luminescence properties. Moreover, this highly transparent glass enables performant X-ray imaging and low-loss waveguiding in fibers drawn above the glass transition. The discovery of "nanocluster glass" opens avenues for unraveling glass formation mechanisms and designing novel luminescent glasses of well-defined building blocks for advanced photonics.

High-Efficiency Circularly Polarized Light-Emitting Diodes Based on Chiral Metal Nanoclusters.

Circularly polarized light-emitting diodes (CP-LEDs) are critical for next-generation optical technologies, ranging from holography to quantum information processing. Currently deployed chiral luminescent materials, with their intricate synthesis and processing and limited efficiency, are the main bottleneck for CP-LEDs. Chiral metal nanoclusters (MNCs) are potential CP-LED materials, given their ease of synthesis and processability as well as diverse structures and excited states. However, their films are usually plagued by inferior electronic quality and aggregation-caused photoluminescence quenching, necessitating their incorporation into host materials; without such a scheme, MNC-based LEDs exhibit external quantum efficiencies (EQEs) < 10%. Herein, we achieve an efficiency leap for both CP-LEDs and cluster-based LEDs by using novel chiral MNCs with aggregation-induced emission enhancement. CP-LEDs using enantiopure MNC films attain EQEs of up to 23.5%. Furthermore, by incorporating host materials, the devices yield record EQEs of up to 36.5% for both CP-LEDs and cluster-based LEDs, along with electroluminescence dissymmetry factors (|gEL|) of around 1.0 × 10-3. These findings open a new avenue for advancing chiral light sources for next-generation optoelectronics.

Engineering Metal-Organic Frameworks with Tunable Colors for High-Performance Wireless Communication.

Metal-organic frameworks (MOFs) have emerged as excellent platforms possessing tunable and controllable optical behaviors that are essential in high-speed and multichannel data transmission in optical wireless communications (OWCs). Here, we demonstrate a novel approach to achieving a tunable wide modulation bandwidth and high net data rate by engineering a combination of organic linkers and metal clusters in MOFs. More specifically, two organic linkers of different emission colors, but equal molecular length and connectivity, are successfully coordinated by zirconium and hafnium oxy-hydroxy clusters to form the desired MOF structures. The precise change in the interactions between these different organic linkers and metal clusters enables control over fluorescence efficiency and excited state lifetime, leading to a tunable modulation bandwidth from 62.1 to 150.0 MHz and a net data rate from 303 to 363 Mb/s. The fabricated color converter MOFs display outstanding performance that competes, and in some instances surpasses, those of conventional materials commonly used in light converter devices. Moreover, these MOFs show high practicality in color-pure wavelength-division multiplexing (WDM), which significantly improved the data transmission link capacity and security by the contemporary combining of two different data signals in the same path. This work highlights the potential of engineered MOFs as a game-changer in OWCs, with significant implications for future high-speed and secure data transmission.

Multifunctional difluoroboron ß-diketonate-based luminescent receiver for a high-speed underwater wireless optical communication system.

The last decade has witnessed considerable progress in underwater wireless optical communication in complex environments, particularly in exploring the deep sea. However, it is difficult to maintain a precise point-to-point reception at all times due to severe turbulence in actual situations. To facilitate efficient data transmission, the color-conversion technique offers a paradigm shift in large-area and omnidirectional light detection, which can effectively alleviate the étendue limit by decoupling the field of view and optical gain. In this work, we investigated a series of difluoroboron ß-diketonate fluorophores by measuring their photophysical properties and optical wireless communication performances. The emission colors were tuned from blue to green, and >0.5 Gb/s data transmission was achieved with individual color channel in free space by implementing an orthogonal frequency-division multiplexing (OFDM) modulation scheme. In the underwater experiment, the fluorophore with the highest transmission speed was fabricated into a 4×4 cm2 luminescent concentrator, with the concentrated emission from the edges coupled with an optical fiber array, for large-area photodetection and optical beam tracking. The net data rates of 130 Mb/s and 217 Mb/s were achieved based on nonreturn- to-zero on-off keying and OFDM modulation schemes, respectively. Further, the same device was used to demonstrate the linear light beam tracking function with high accuracy, which is beneficial for sustaining a reliable and stable connection in a dynamic, turbulent underwater environment.

Quantum Tunneling Effect in CsPbBr3 Multiple Quantum Wells.

Two-dimensional (2D) lead halide perovskites (LHPs) have garnered incredible attention thanks to their exciting optoelectronic properties and intrinsic strong quantum confinement effect. Herein, we carefully investigate and decipher the charge carrier dynamics at the interface between CsPbBr3 multiple quantum wells (MQWs) as the photoactive layer and TiO2 and Spiro-OMeTAD as electron and hole transporting materials, respectively. The fabricated MQWs comprise three monolayers of CsPbBr3 separated by 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) as barriers. By varying the BCP thickness, we show that charge carrier extraction from MQWs to the corresponding extracting layer occurs through a quantum tunneling effect, as elaborated by steady-state and time-resolved photoluminescence measurements and further verified by femtosecond transient absorption experiments. Ultimately, we have investigated the impact of the barrier-thickness-dependent quantum tunneling effect on the photoelectric behavior of the synthesized QW photodetector devices. Our findings shed light on one of the most promising approaches for efficient carrier extraction in quantum-confined systems.

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry.

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58 H20 PET36 (PPh3 )4 ]2+ (Cu58 ; PET: phenylethanethiolate; PPh3 : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into the surface-defective analog [Cu57 H20 PET36 (PPh3 )4 ]+ (Cu57 ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57 . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58 , Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts.

Metal-Organic Frameworks in Mixed-Matrix Membranes for High-Speed Visible-Light Communication.

Mixed-matrix membranes (MMMs) based on luminescent metal-organic frameworks (MOFs) and emissive polymers with the combination of their unique advantages have great potential in separation science, sensing, and light-harvesting applications. Here, we demonstrate MMMs for the field of high-speed visible-light communication (VLC) using a very efficient energy transfer strategy at the interface between a MOF and an emissive polymer. Our steady-state and ultrafast time-resolved experiments, supported by high-level density functional theory calculations, revealed that efficient and ultrafast energy transfer from the luminescent MOF to the luminescent polymer can be achieved. The resultant MMMs exhibited an excellent modulation bandwidth of around 80 MHz, which is higher than those of most well-established color-converting phosphors commonly used for optical wireless communication. Interestingly, we found that the efficient energy transfer further improved the light communication data rate from 132 Mb/s of the pure polymer to 215 Mb/s of MMMs. This finding not only showcases the promise of the MMMs for high-speed VLC but also highlights the importance of an efficient and ultrafast energy transfer strategy for the advancement of data rates of optical wireless communication.

Access to Highly Efficient Energy Transfer in Metal-Organic Frameworks via Mixed Linkers Approach.

Herein, we report a new light-harvesting mixed-ligand Zr(IV)-based metal-organic framework (MOF),with underlying fcu topology, encompassing the [Zr6(µ3-O)4(µ3-OH)4(O2C-)12] cluster and an equimolar mixture of thiadiazole- and benzimidazole-functionalized ligands. The successful integration of ligands with similar structural features but with notable chemical distinction afforded the attainment of a highly efficient energy transfer (ET). Notably, the very strong spectral overlap between the emission spectrum of benzimidazole (energy donor) and the absorption spectrum of thiadiazole (energy acceptor) provided an ideal platform to achieve very rapid (picosecond time scale) and highly efficient energy transfer (around 90% efficiency), as evidenced by time-resolved spectroscopy. Remarkably, the ultrafast time-resolved experiments quantified for the first time the anticipated close proximity of the two linkers with an average distance of 17 Å. This finding paves the way for the design and synthesis of periodic MOFs affording very efficient and fast ET to mimic natural photosynthetic systems.

Correlation of Photoluminescence and Structural Morphologies at the Individual Nanoparticle Level.

Single-particle spectroscopy has demonstrated great potential for analyzing the microscopic behavior of various nanoparticles (NPs). However, high-resolution optical imaging of these materials at the nanoscale is still very challenging. Here, we present an experimental setup that combines high sensitivity of time-correlated single-photon counting (TCSPC) techniques with atomic force microscopy (AFM). This system enables single-photon detection with a time resolution of 120 ps and a spatial resolution of 5 nm. We utilize the setup to investigate the photoluminescence (PL) characteristics of both zero-dimensional (0D) and three-dimensional (3D) perovskite nanocrystals and establish a correlation between the particles' sizes, their PL blinking, and the lifetime behavior. Our system demonstrates an unprecedented level of information, opening the door to understanding the morphology-luminescence correlation of various nanosystems.

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View.

Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time-resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn-Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S0 →S1 ), a metal-to-ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S1 →T2 →T1 ), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇2 ρ(r) and ∇2 Vne (r)) during the deactivation path. This polarization increases the magnitude of the intra-atomic nuclear-electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand.

Ultrafast excited state hydrogen atom transfer in salicylideneaniline driven by changes in aromaticity.

We investigated two important unresolved issues on excited state intramolecular proton transfer (ESIPT) reactions, i.e., their driving force and the charge state of the transferred species by means of quantum chemical topology. We related changes in the aromaticity of a molecule after electron excitation to reaction dynamics in an excited state. Additionally, we found that the conveyed particle has a charge intermediate between that of a bare proton and a neutral hydrogen atom. We anticipate that the analysis presented in this communication will yield valuable insights into ESIPT and other similar photochemical reactions.

Real-Time Tracking of Hot Carrier Injection at the Interface of FAPbBr3 Perovskite Using Femtosecond Mid-IR Spectroscopy.

One of the most effective approaches to optimizing the performance of perovskite solar cells is to fully understand the ultrafast carrier dynamics at the interfaces between absorber and transporting layers at both the molecular and atomic levels. Here, the injection dynamics of hot and relaxed charge carriers at the interface between the hybrid perovskite, formamidinium lead bromide (FAPbBr3), and the organic electron acceptor, IEICO-4F, are investigated and deciphered by using femtosecond (fs) mid-infrared (IR), transient absorption (TA), and fluorescence spectroscopies. The visible femtosecond-TA measurements reveal the generation of hot carriers and their transition to free carriers in the pure FAPbBr3 film. Meanwhile, the efficient extraction of hot carriers in the mixed FAPbBr3/IEICO-4F film is clearly evidenced by the complete disappearance of their spectral signature. More specifically, the time-resolved results reveal that hot carriers are injected from FAPbBr3 to IEICO-4F within 150 fs, while the transfer time for the relaxed carriers is about 205 fs. The time-resolved mid-IR experiments also demonstrate the ultrafast formation of two peaks at 2115 and 2233 cm-1, which can be attributed to the C≡N symmetrical and asymmetrical vibrational modes of anionic IEICO-4F, thus providing crystal clear evidence for the electron transfer process between the donor and acceptor units. Moreover, photoluminescence (PL) lifetime measurements reveal an approximately 10-fold decrease in the donor lifetime in the presence of IEICO-4F, thereby confirming the efficient electron injection from the perovskite to the acceptor unit. In addition, the efficient electron injection at the FAPbBr3/IEICO-4F interface and its impact on the C≡N bond character are experimentally evidenced and align with density functional theory (DFT) calculations. This work offers new insights into the electron injection process at the FAPbBr3/IEICO-4F interface, which is crucial for developing efficient optoelectronic devices.

Enhancing the Sensitivity and Spatial Imaging Resolution of a Hybrid X-Ray Imaging Screen via Energy Transfer at the ZnS (Ag) and a Thermally Activated Delayed Fluorescence Interface.

Novel scintillation materials have played an indispensable role in the recent remarkable progress witnessed for X-ray imaging technology. Herein, a high-performance X-ray scintillation screen was developed based on a highly efficient hybrid system combining inorganic ZnS (Ag) with thermally activated delayed fluorescence (TADF) scintillator materials via an interfacial energy transfer (EnT) mechanism. ZnS (Ag) has a high X-ray absorption capacity and functions as the initial layer for efficiently converting high-energy X-ray photons into low-energy visible light (acting as a sensitizer) while also serving as an energy donor. The TADF component, on the contrary, is an energy acceptor and forms an active scintillating layer. By harnessing TADF chromophores that can efficiently capture both singlet and triplet excitons, our composite material offers a remarkable spatial imaging resolution of 24 line pairs per millimeter, surpassing those of the majority of existing organic and inorganic scintillators. Further, our interfacial energy transfer strategy effectively amplifies the radioluminescence intensity of the TADF scintillator by a factor of 75, offering an outstanding light yield of 38,000 photons/MeV. This advancement represents a remarkable breakthrough in organic X-ray scintillation technology and is a notable achievement within the X-ray imaging field, paving the way for novel applications in medical imaging and security inspection.

Leveraging Intermolecular Charge Transfer for High-Speed Optical Wireless Communication.

Intermolecular charge transfer (CT) complexes have emerged as versatile platforms with customizable optical properties that play a pivotal role in achieving tunable photoresponsive materials. In this study, we introduce an innovative approach for enhancing the modulation bandwidth and net data rates in optical wireless communications (OWCs) by manipulating combinations of monomeric molecules within intermolecular CT complexes. Concurrently, we extensively investigate the intermolecular charge transfer mechanism through diverse steady-state and ultrafast time-resolved spectral techniques in the mid-infrared range complemented by theoretical calculations using density functional theory. These intermolecular CT complexes empower precise control over the -3 dB bandwidth and net data rates in OWC applications. The resulting color converters exhibit promising performance, achieving a net data rate of ∼100 Mb/s, outperforming conventional materials commonly used in the manufacture of OWC devices. This research underscores the substantial potential of engineering intermolecular charge transfer complexes as an ongoing progression and commercialization within the OWC. This carries profound implications for future initiatives in high-speed and secure data transmission, paving the way for promising endeavors in this area.

Controlled Synthesis of Terbium-Doped Colloidal Gd2O2S Nanoplatelets Enables High-Performance X-ray Scintillators.

Terbium-doped gadolinium oxysulfide (Gd2O2S:Tb3+), commonly referred to as Gadox, is a widely used scintillator material due to its exceptional X-ray attenuation efficiency and high light yield. However, Gadox-based scintillators suffer from low X-ray spatial resolution due to their large particle size, which causes significant light scattering. To address this limitation, we report the synthesis of terbium-doped colloidal Gadox nanoplatelets (NPLs) with near-unity photoluminescence quantum yield (PLQY) and high radioluminescence light yield (LY). In particular, our investigation reveals a strong correlation between PLQY, LY, particle size, and Tb3+concentration. Our synthetic approach allows precise control over the lateral size and thickness of the Gadox NPLs, resulting in a LY of 50,000 photons/MeV. Flexible scintillating screens fabricated with the solution-processable Gadox NPLs exhibited a 20 lp/mm X-ray spatial resolution, surpassing commercial Gadox scintillators. These high-performance and flexible Gadox NPL-based scintillators enable enhanced X-ray imaging capabilities in medicine and security. Our work provides a framework for designing nanomaterial scintillators with superior spatial resolution and efficiency through precise control of dimensions and dopant concentration.

Singlet Fission-Based High-Resolution X-Ray Imaging Scintillation Screens.

X-ray imaging technology is critical to numerous different walks of daily life, ranging from medical radiography and security screening all the way to high-energy physics. Although several organic chromophores are fabricated and tested as X-ray imaging scintillators, they generally show poor scintillation performance due to their weak X-ray absorption cross-section and inefficient exciton utilization efficiency. Here, a singlet fission-based high-performance organic X-ray imaging scintillator with near unity exciton utilization efficiency is presented. Interestingly, it is found that the X-ray sensitivity and imaging resolution of the singlet fission-based scintillator are dramatically improved by an efficient energy transfer from a thermally activated delayed fluorescence (TADF) sensitizer, in which both singlet and triplet excitons can be efficiently harnessed. The fabricated singlet fission-based scintillator exhibits a high X-ray imaging resolution of 27.5 line pairs per millimeter (lp mm-1 ), which exceeds that of most commercial scintillators, demonstrating its high potential use in medical radiography and security inspection.

Zero-dimensional Cu(I)-based organometallic halide with green cluster-centred emission for high resolution X-ray imaging screens.

In this communication, we report a low-dimensional perovskite-related structure based on Cu(I) organometallic halide with strong green cluster-centred emission and near-unity photoluminescence quantum yield. The 0D [Rb(18-crown-6)]2Cu4I6 was sucessfully applied for X-ray imaging screens which exhibit high spatial resolution of 16.8 lp mm-1 and low detection limit of 458 nGy s-1.

TADF-Based X-ray Screens with Simultaneously Efficient Singlet and Triplet Energy Transfer for High Spatial Imaging Resolution.

X-ray imaging scintillators play a crucial role in medical examinations and safety inspections, making them an essential technology in our modern lives. However, commercially available high-performance scintillators are fabricated exclusively from ceramic materials that require harsh preparation conditions and are costly to produce. Organic scintillators have emerged as a promising alternative due to their transparency and ease of fabrication at a low cost. Unfortunately, organic scintillators suffer from inefficient exciton utilization efficiency, leading to poor performance in X-ray imaging screens and hindering their commercialization. In this study, we explore the use of thermally activated delayed fluorescence (TADF) chromophores (4CzIPN-I and 4CzTPN) to enhance the absorption of ionizing radiation in X-ray imaging screens by an order of magnitude. By leveraging the unique features of TADF chromophores through simultaneously singlet-singlet and triplet-triplet efficient energy transfers at the interface between two different TADF systems, we demonstrate an impressive X-ray sensitivity and radioluminescence intensity. Our time-resolved experiments and density functional theory (DFT) calculations provide further evidence for the effectiveness of this approach. The resulting X-ray imaging screens based on this efficient interfacial energy transfer process in TADF systems exhibit outstanding X-ray imaging resolution of 20 line pairs/mm, the highest resolution reported thus far for organic scintillators. This resolution is at least two times higher than that achieved by commonly used commercial inorganic scintillators in the X-ray imaging market. These findings introduce a new component for greatly improving the performance of organic X-ray imaging scintillators, supporting a wide range of emerging X-ray applications with exceptional spatial resolution.

Phonon-driven transient bandgap renormalization in perovskite single crystals.

Tailoring the electronic structure of perovskite materials on ultrafast timescales is expected to shed light on optimizing optoelectronic applications. However, the transient bandgap renormalization observed upon photoexcitation is commonly explained by many-body interactions of optically created electrons and holes, which shrink the original bandgap by a few tens of millielectronvolts with a sub-picosecond time constant, while the accompanying phonon-induced effect remains hitherto unexplored. Here we unravel a significant contribution of hot phonons in the photo-induced transient bandgap renormalization in MAPbBr3 single crystals, as evidenced by asymmetric spectral evolutions and transient reflection spectral shifts in the picosecond timescale. Moreover, we performed a spatiotemporal study upon optical excitation with time-resolved scanning electron microscopy and identified that the surface charge carrier diffusion and transient bandgap renormalization are strongly correlated in time. These findings highlight the need to re-evaluate current theories on photo-induced bandgap renormalization and provide a new approach for precisely controlling the optical and electronic properties of perovskite materials, enabling the design and fabrication of high-performance optoelectronic devices with exceptional efficiency and unique properties.

Tunable Photoinduced Charge Transfer at the Interface between Benzoselenadiazole-Based MOF Linkers and Thermally Activated Delayed Fluorescence Chromophore.

Structural modifications to molecular systems that lead to the control of photon emission processes at the interfaces between photoactive materials play a key role in the development of fluorescence sensors, X-ray imaging scintillators, and organic light-emitting diodes (OLEDs). In this work, two donor-acceptor systems were used to explore and reveal the effects of slight changes in chemical structure on interfacial excited-state transfer processes. A thermally activated delayed fluorescence (TADF) molecule was chosen as the molecular acceptor. Meanwhile, two benzoselenadiazole-core MOF linker precursors, Ac-SDZ and SDZ, with the presence and absence of a C≡C bridge, respectively, were carefully chosen as energy and/or electron-donor moieties. We found that the SDZ -TADF donor-acceptor system exhibited efficient energy transfer, as evidenced by steady-state and time-resolved laser spectroscopy. Furthermore, our results demonstrated that the Ac-SDZ-TADF system exhibited both interfacial energy and electron transfer processes. Femtosecond-mid-IR (fs-mid-IR) transient absorption measurements revealed that the electron transfer process takes place on the picosecond timescale. Time-dependent density functional theory (TD-DFT) calculations confirmed that photoinduced electron transfer occurred in this system and demonstrated that it takes place from C≡C in Ac-SDZ to the central unit of the TADF molecule. This work provides a straightforward way to modulate and tune excited-state energy/charge transfer processes at donor-acceptor interfaces.