An efficient strategy is reported to achieve rewritable and multi-level security printing based on the emission intensity and lifetime switching caused by manipulating the dynamic ionic coordination of Mn(II) complexes. Confidential information can be repeatedly printed on the fabricated security paper by controlling the dynamic ionic interaction of Mn(II) complexes. Moreover, multilevel security printing has been achieved through dynamically tuning the emission lifetimes of the Mn(II) complexes.

Photochemical reactions at lower energy than the absorption window are currently achieved by multi-photon processes, including two-photon absorption and photon upconversion, which have limited energy utilization efficiency. Here, we report a one-photon strategy based on triplet−triplet energy transfer (TTET) between a photosensitizer and a photocleavable molecule to achieve photolysis at low energy. To verify this concept, we chose platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP) as the photosensitizer and synthesized a boron-dipyrromethene (BODIPY)-based prodrug as the photocleavable molecule. Photolysis of the prodrug is achieved by TTET upon excitation of PtTPBP at 625 nm with a photolysis quantum yield of 2.8%. Another demonstration shows an unexpected higher photolysis quantum yield than the direct excitation at 530 nm. This strategy opens a new path for achieving photolysis at long wavelengths, benefiting the applications in biological studies, photopharmacology, and photoresponsive drug delivery.

coupling effect induced by heavy-metal atoms. [5,6] For example, noble metal-based phosphors including iridium(III) complexes, [7][8][9][10][11][12][13][14][15][16] platinum(II) complexes, [17][18][19][20] and gold(III) complexes [21,22] have been widely used in phosphorescent OLEDs (PhOLEDs). However, these noble metals suffer from the low abundance and high cost. Hence, the relatively abundant, lowcost, and low-toxic phosphorescent metal complex have been drawing great interests for PhOLEDs.Recent explorations of phosphorescent manganese(II) complexes appear to be a new and attractive alternative toward highly efficient PhOLEDs. The manganese(II) complexes display strong photoluminescence in solid state originating from the metal-centered d-d ( 4 T 1 (G) → 6 A 1 ) radiative transition. [23][24][25] The well-known green light-emitting manganese(II) complexes are ionic compounds consisting of organic cations and inorganic tetrahalogenomanganate(II) anions. [26,27] Attributed to their excellent solid-state photophysical properties, this kind of organic-inorganic hybrid complexes have exhibited promising optoelectronic applications. For example, Chen and co-workers have realized the solution-processed PhOLEDs based on the ionic tetrabromide manganese(II) complex ((Ph 4 P) 2 (MnBr 4 )) as an emitting dopant, the external quantum efficiency (EQE) of this device can reach 9.6% for the doped OLEDs. [28] However, the ionic manganese(II) complexes often suffer from low stability and can be easily hydrolyzed Phosphorescent transition-metal complexes have played the vital role in the rapid development of organic light-emitting diodes (OLEDs) as the most promising candidates for next-generation flat-panel display and solid-state lighting techniques. In this work, novel and low-cost phosphorescent neutral tetrahedral manganese(II) complexes (DBFDPO-MnX 2 , X = Br, or Cl) based on dibenzofuran-based phosphine oxide derivative as ligand are designed and synthesized. The manganese(II) complexes exhibit intense green phosphorescence with high photoluminescence quantum yields (PLQYs) of as high as 81.4% (DBFDPO-MnBr 2 ). Using complex DBFDPO-MnBr 2 as dopant, a green OLED with current efficiency (CE max ) of 35.47 cd A −1 , power efficiency (PE max ) of 34.35 lm W −1 , and external quantum efficiency (EQE max ) of 10.49% is fabricated. Interestingly, red exciplex emission is also observed in electroluminescence, arising from the interaction between the host materials (bis(2-(2-hydroxyphenyl)-pyridine)beryllium (Bepp 2 ) or 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene (TPBi)) and the dopant (DBFDPO-MnBr 2 ).The exciplex-based red OLED in this study exhibits the maximum CE and PE reaching 18.64 cd A −1 and 17.92 lm W −1 , respectively, which are among the up-to-date highest values for exciplex-based red OLEDs. Beneficial from the exciplex, it has the great potential to broaden the electroluminescent spectra with manganese(II) complex. Phosphorescent OLEDsThe ORCID identification number(s) for the author(s) of this article can be fou...

bioimaging, [3] and anti-counterfeiting applications. [4] Pure organic OPRTP materials are more attractive compared to the transition metal or rare earth-based phosphorescent materials owing to their low production cost, easy synthesis, low toxicity, and good flexibility. [5] However, OPRTP is rare in pure organic molecules because of the forbidden transition from singlet to triplet excited states. The reported metal-free OPRTP materials are usually substituted with aromatic carbonyl groups [6] or heavy atoms [7] to facilitate the intersystem crossing (ISC) process, while crystallization, [8] host-guest interaction, [9] and polymer doping [10] are utilized to suppress the nonradiative decay and stabilize the triplet states.Solid-state phosphorescence is highly dependent on molecular stacking, such as aggregation-caused quenching. [11] Recently, OPRTP has been observed in H- [8a] or J-aggregates, [12] while the influence of T-shaped (edge-to-face) arrangement on phosphorescence has been rarely discussed. Published work mainly focused on the stabilization of triplet excited states by molecular packing, but packing-induced intermolecular charge transfer received less attention in OPRTP materials although it strongly affected ISC efficiency and the energy gap (ΔE ST ) between singlet and triplet excited states. [3c,13] Polycyclic π-conjugated compounds, such as indolo[3,2-b] carbazoles (ICZs) and their analogues, are important organic semiconductors, which have been widely used in organic optoelectronic fields, such as organic field-effect transistors and photovoltaic cells, owing to their excellent carrier transporting properties. [14] In this work, 6,12-diphenyl-5,6,11,12tetrahydroindolo[3,2-b]carbazole (Ben-H, Figure 1), one of the ICZ analogues, unexpectedly exhibited OPRTP after the cease of UV light irradiation. Unlike most reported OPRTP materials, there were no commonly used groups such as aromatic carbonyl groups or heavy atoms in Ben-H. Based on the energy level diagram and single-crystal structure of Ben-H, we hypothesized that charge transfer (CT) played a dominant role in persistent emission (Figure 2). In the isolated molecular state, intramolecular charge transfer (ICT) from the indole rings to the benzene rings gave rise to the ISC process with narrow ΔE ST energy gap, while in the dimers, T-shaped CH···π interactions induced Organic persistent room-temperature phosphorescence (OPRTP) materials show great prospects in optoelectronic and biomedical applications, such as display, anti-counterfeiting, sensing, and bioimaging. However, the reported OPRTP material systems are relatively rare, and it is a challenge to achieve the tunability of OPRTP. In this work, a series of polycyclic luminophores are developed based on an indole derivative (6,12-diphenyl-5,6,11,12tetrahydroindolo[3,2-b] carbazole, Ben-H) as the structural skeleton. These compounds unexpectedly exhibit dual OPRTP at 442 to 623 nm with lifetimes spanning from 2 to 759 ms. Experimental data and theoretical calculations suggest th...

Pure organic materials with tunable room temperature phosphorescence (RTP) have attracted considerable interest because they are promising candidates for a wide range of optoelectronic applications. Herein, a series of organic compounds of (4‐(9H‐carbazol‐9‐yl)butyl) triphenylphosphonium (CBTP) with different halide anions (CBTP‐Cl, CBTP‐Br, and CBTP‐I) are synthesized. They show emission color changes from blue to orange‐red in the solid state. Single‐crystal X‐ray diffraction analysis and theoretical calculations demonstrate that the RTP is primarily caused by the external heavy‐atom effect (EHE), which enhances the spin–orbit coupling between the singlet and triplet excited states to facilitate the intersystem crossing rate. Distinct white light emission can be achieved using the controllable RTP by doping a certain ratio of potassium iodide (KI) into a polymer matrix containing CBTP‐Cl. Moreover, luminescent information can be recorded on a paper substrate made from a polymer film containing CBTP‐Cl with KI aqueous solution as the ink. The results suggest that rational control of the EHE of these pure organic materials is promising for different optoelectronic applications, including solid‐state lighting, data recording, and security protection.

The development of metallacycles with high stability and intense near-infrared (NIR) absorption is important for biomedical applications. However, very few molecular design strategies have been developed on such metallacycles. Herein, we report a new series of stable and well-defined NIR-absorbing metallacycles (M1–M3) through the Pt–acetylide coordination with highly efficient photoconversion performance for cancer phototherapy. The metallacycles showed high stability and strong NIR absorption, and the absorption peaks were red shifted approximately 30 nm in comparison with their corresponding precursors. The introduction of Pt into metallacycles promotes significant photoconversions, including the singlet-to-triplet and nonradiative transitions. Moreover, the fabricated M3 nanoparticles (M3-NPs) showed favorable photoconversions into both thermal effect and singlet oxygen generation upon NIR irradiation, achieving tumor ablation. This novel design of Pt-acetylide metallacycles possesses not only complex topological architectures but also a valuable paradigm for precise cancer phototherapy, which is important for grafting stimuli-responsive functional groups into metallacycles for the development of high-performance biomedical supramolecular materials.

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Scintillator‐based X‐ray imaging has attracted great attention from industrial quality inspection and security to medical diagnostics. Herein, a series of lanthanide(III)‐Cu4I4 heterometallic organic frameworks (Ln‐Cu4I4 MOFs)‐based X‐ray scintillators are developed by rationally assembling X‐ray absorption centers ([Cu4I4] clusters) and luminescent chromophores (Ln(III) ions) in a specific manner. Under X‐ray irradiation, the heavy inorganic units ([Cu4I4] clusters) absorb the X‐ray energy to populate triplet excitons via halide‐to‐ligand charge transfer (XLCT) combined with the metal‐to‐ligand charge‐transfer (MLCT) state (defined as the X/MLCT state), and then the 3X/MLCT excited state sensitizes Tb3+ for intense X‐ray‐excited luminescence via excitation energy transfer. The obtained Tb‐Cu4I4 MOF scintillators exhibit high resistance to humidity and radiation, excellent linear response to X‐ray dose rate, and high X‐ray relative light yield of 29 379 ± 3000 photons MeV−1. The relative light yield of Tb‐Cu4I4 MOFs is ≈3 times higher than that of the control Tb(III) complex. X‐ray imaging tests show that the Tb‐Cu4I4 MOFs‐based flexible scintillator film exhibits a high spatial resolution of 12.6 lp mm−1. These findings not only provide a promising design strategy to develop lanthanide‐MOF‐based scintillators with excellent scintillation performance, but also exhibit high‐resolution X‐ray imaging for biological specimens and electronic chips.