Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection. D ata recording, storage and security technologies have been widely utilized in economic and military fields as well as in our daily life. Smart luminescent materials that are responsive to external stimuli have received considerable attention in the construction of optical data recording and storage devices [1][2][3][4][5] . These materials have been classified on the basis of the types of external stimuli that they are responsive to. Mechanochromic materials show changes in emission colour in the presence of mechanical stimuli (for example, shearing, grinding and rubbing) because of the interruption of intermolecular interactions (for example, p-p stacking and hydrogen bonds) [6][7][8][9][10] . Vapochromic luminescence has been observed in materials that are responsive to volatile organic compounds 11,12 . Electric field is an important external stimulus. Electrochromism occurs in p-conjugated polymers because of the reversible transition between two redox states [13][14][15][16] . However, materials showing electrochromic luminescence, which is distinct luminescence colour responses to an electric field, are scarce. We envision the potential commercial applications of electrochromic luminescent materials because they can be conveniently integrated into semiconductor-based electronic devices. In addition, it is conceivable that compounds simultaneously showing mechanochromic, vapochromic and electrochromic luminescence are of great use to the development of multifunctional materials.Phosphorescent transition-metal complexes, such as those of Ir(III) and Pt(II), have been extensively studied for various photonic and electronic applications because of their rich excited-state properties, including high luminescence quantum yields, long emission lifetimes, large Stokes shifts, high photostability and various luminescence colours [17][18][19][20] . These complexes have also been utilized a...
Organelle-targeted photosensitizers have been reported to be effective photodynamic therapy (PDT) agents. In this work, we designed and synthesized two iridium(III) complexes that specifically stain the mitochondria and lysosomes of living cells, respectively. Both complexes exhibited long-lived phosphorescence, which is sensitive to oxygen quenching. The photocytotoxicity of the complexes was evaluated under normoxic and hypoxic conditions. The results showed that HeLa cells treated with the mitochondria-targeted complex maintained a slower respiration rate, leading to a higher intracellular oxygen level under hypoxia. As a result, this complex exhibited an improved PDT effect compared to the lysosome-targeted complex, especially under hypoxia conditions, suggestive of a higher practicable potential of mitochondria-targeted PDT agents in cancer therapy.
A type I Ru(ii) photosensitizer retained an excellent PDT effect under hypoxia through the formation of highly-oxidative hydroxyl radicals under light irradiation.
Flexible electronics, which can be distributed on any surface we need, are highly demanded in the development of Internet of Things (IoT), robot technology and electronic skins. Temperature is a fundamental physical parameter, and it is an important indicator in many applications. Therefore, a flexible temperature sensor is required. Here, we report a simple method to fabricate three lightweight, low-cost and flexible temperature sensors, whose sensitive materials are reduced graphene oxide (r-GO), single-walled carbon nanotubes (SWCNTs) and multi-wall carbon nanotubes (MWCNTs). By comparing linearity, sensitive and repeatability, we found that the r-GO temperature sensor had the most balanced performance. Furthermore, the r-GO temperature sensor showed good mechanical properties and it could be bent in different angles with negligible resistance change. In addition, the performance of the r-GO temperature sensor remained stable under different kinds of pressure and was unaffected by surrounding environments, like humidity or other gases, because of the insulating layer on its sensitive layer. The easy-fabricated process and economy, together with the remarkable performance of the r-GO temperature sensor, suggest that it is suitable for use as a robot skin or used in the environment of IoT.
Scheme 1. The structures of closo-carborane-functionalized facial and meridional iridium(III) 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.
Molecular oxygen (O2) plays a key role in many physiological processes, and becomes a toxicant to kill cells when excited to 1O2. Intracellular O2 levels, or the degree of hypoxia, are always viewed as an indicator of cancers. Due to the highly efficient cancer therapy ability and low side effect, photodynamic therapy (PDT) becomes one of the most promising treatments for cancers. Herein, an early‐stage diagnosis and therapy system is reported based on the phosphorescent conjugated polymer dots (Pdots) containing Pt(II) porphyrin as an oxygen‐responsive phosphorescent group and 1O2 photosensitizer. Intracellular hypoxia detection has been investigated. Results show that cells treated with Pdots display longer lifetimes under hypoxic conditions, and time‐resolved luminescence images exhibit a higher signal‐to‐noise ratio after gating off the short‐lived background fluorescence. Quantification of O2 is realized by the ratiometric emission intensity of phosphorescence/fluorescence and the lifetime of phosphorescence. Additionally, the PDT efficiency of Pdots is estimated by flow cytometry, MTT cell viability assay, and in situ imaging of PDT induced cell death. Interestingly, Pdots exhibit a high PDT efficiency and would be promising in clinical applications.
Tungsten disulfide (WS 2 ) nanosheets (NSs) have become a promising room-temperature gas sensor candidate due to their inherent high surface-to-volume ratio, tunable electrical properties, and high on-state current density. For further practical applications of WS 2 -based gas sensors, it is still necessary to overcome the insensitive response and incomplete recovery at room temperature. In this work, we controllably synthesized high-performance ammonia (NH 3 ) gas sensor based on CuO decorated WS 2 NSs. The optimized p-p WS 2 /CuO heterojunctions improve the surface catalytic effect, thereby enhancing the gas-sensing performance. The pure WS 2 NSs-based gas sensors showed a low response and an incomplete recovery in the case of NH 3 sensing. After the functionalization of CuO nanoparticles, the WS 2 /CuO heterostructurebased gas sensor exhibits an improved response value of 40.5% to 5 ppm NH 3 and full recoverability without any external assistance. Density functional theory calculations illustrate that the adsorption of CuO for NH 3 is much superior to WS 2 . The p-p heterojunctions strategy demonstrated in this work has great potential in the design of sensitive materials for gas sensors, and provides useful guidance for enhancing the room-temperature sensitivity and recoverability.
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