The one- and two-photon luminescence of stilbene-type solid-state materials can be tuned and controlled from blue to yellow color by a supramolecular cocrystal method.
Tuning and controlling the luminescent properties of molecular materials by changing the orientation and arrangement of the fluorophores within a solid has played an important role in realizing multi-color emission. The formation of polymorphs and multi-component molecular solids have attracted considerable interest as new ways of achieving controllable luminescence and other photophysical properties for application in the next generation of photofunctional materials. In this article, recent advances in the synthesis of fluorescent polymorphs and multi-component materials and potential photo-related applications of the resulting materials are described. We first review the methods of preparation of polymorphs with tunable static luminescence, and the switching of the dynamic luminescence between polymorphs for potential sensor applications is also introduced. Attention is then focused on the supramolecular design (making use of hydrogen bonding and halogen bonding interactions) and methods of fabrication of multi-component molecular solids, and their color-tunable fluorescence and phosphorescence together with their stimuli-responsive properties for use as sensors.The use of density functional theory to study intramolecular and intermolecular energy transfer as well as the electronic structures of multi-component molecular solids is also outlined. Finally, we briefly discuss perspectives for the further development of these luminescent molecular solid-state materials.
Dongpeng Yan obtained hisPhD degree under the supervision of Prof. Xue Duan at Beijing University of Chemical Technology (BUCT) in 2012, In 2011, as a visiting student, he studied at the Department of Chemistry, University of Cambridge under Prof. William Jones. Now he is an associate professor at BUCT. His main research topics are experimental and computer simulation studies of organic photofunctional crystals and new layered materials. He was received an Award Nomination of Annual Figure among Chinese University Students (2011), a "Talent Model" Award in the Universities in Beijing (2010), the Tang Aoqing Chemical Scholarship (2011), and many other awards. David G. Evans studied as both undergraduate and research student at Jesus College, Oxford and obtained a DPhil under the supervision of Prof. D. M. P. Mingos FRS. Aer postdoctoral work at Bristol University with Prof. F. G. A. Stone FRS, he was appointed to a lectureship at Exeter University in 1985. Several visits to Chinese university chemistry departments in the early 1990s convinced him of China's great potential for development in this area and he moved to Beijing University of Chemical Technology in 1996. His research interests focus on intercalation in layered solids. He was awarded an International Scientic and Technological Cooperation Award of the People's Republic of China in 2005.
We report that two types of Zn-terephthalate (TPA) MOFs (namely [Zn(TPA)(DMF)] (1-DMF) and MOF-5) could exhibit an obvious room-temperature afterglow emission with a time-resolved luminescence lifetime as high as 0.47 seconds.
In this review, we summarize recent advances in establishing persistently luminescent materials from the view of examining experimental and theoretical approaches to room-temperature phosphorescence and thermally-activated delayed fluorescence.
The oxygen evolution reaction (OER), as an important process involved in water splitting and rechargeable metal–air batteries, has drawn increasing attention in the context of clean energy generation and efficient energy storage. This review concerns the progress and new discoveries in the field of Ni/Fe‐based micro/nanostructures toward electrochemical and photo‐electrochemical (PEC) water oxidation during last few years. First, toward the design and construction of new electrocatalysis, different types of current Ni/Fe‐based compounds for OER are summarized. The mechanism studies of the active phases and positions of Ni/Fe‐based micro/nanostructures are further introduced to understand the properties of catalytic active sites, which could facilitate further improving the performance of Ni/Fe‐based OER electrocatalysts. Second, splitting water using sunlight with low overpotential is another important target in making solar‐to‐hydrogen micro/nanodevices, and thus attention is then focused on the development of several important Ni/Fe‐based PEC catalysts. Third, the recent theoretical calculations on the OER mechanism during water splitting and insights into electronic structures are analyzed; finally, the future trends and perspectives are also discussed briefly.
Molecular room‐temperature phosphorescent (RTP) materials with long‐lived excited states have attracted widespread attention in the fields of optical imaging, displays, and sensors. However, accessing ultralong RTP systems remains challenging and examples are still limited to date. Herein, a thermally activated delayed fluorescence (TADF)‐assisted energy transfer route for the enhancement of persistent luminescence with an RTP lifetime as high as 2 s, which is higher than that of most state‐of‐the‐art RTP materials, is proposed. The energy transfer donor and acceptor species are based on the TADF and RTP molecules, which can be self‐assembled into two‐component ionic salts via hydrogen‐bonding interactions. Both theoretical and experimental studies illustrate the occurrence of effective Förster resonance energy transfer (FRET) between donor and acceptor molecules with an energy transfer efficiency as high as 76%. Moreover, the potential for application of the donor–acceptor cocrystallized materials toward information security and personal identification systems is demonstrated, benefitting from their varied afterglow lifetimes and easy recognition in the darkness. Therefore, the work described in this study not only provides a TADF‐assisted FRET strategy toward the construction of ultralong RTP, but also yields hydrogen‐bonding‐assembled two‐component molecular crystals for potential encryption and anti‐counterfeiting applications.
Lanthanide metal-organic frameworks (Ln-MOFs) have received much attention owing to their structural tunability and widely photofunctional applications. However, successful examples of Ln-MOFs with well-defined photonic performances at micro-/nanometer size are still quite limited. Herein, self-assemblies of 1,3,5-benzenetricarboxylic acid (BTC) and lanthanide ions afford isostructural crystalline Ln-MOFs. Tb-BTC, Eu@Tb-BTC, and Eu-BTC have 1D microrod morphologies, high photoluminescence (PL) quantum yields, and different emission colors (green, orange, and red). Spatially PL resolved spectra confirm that Ln-MOF microrods exhibit an optical waveguide effect with low waveguide loss coefficient (0.012≈0.033 dB μm ) during propagation. Furthermore, these microrods feature both linear and chiral polarized photoemission with high anisotropy.
Singlet oxygen has won a great deal of attention to catalysis and biological studies due to its strong oxidizing properties. However, the photosensitizers which require for the generation of singlet oxygen remain inadequate because of their lack of long-wavelength absorption, weak hydrophilicity, and poor biocompatibility. Here, we develop near-infrared laser activated supramolecular photosensitizers (isophthalic acid/layered double hydroxide nanohybrids) for efficient two-photon photodynamic therapy. The singlet oxygen quantum yield of nanohybrid is up to 0.74. Critically, in vitro tests verify the superior anti-cancer properties of nanohybrid with an IC50 determine to be 0.153 μg mL−1. The nanohybrids take advantage of the superior tissue penetration of 808 nm laser irradiation and exhibit a dramatically strong ability to ablate tumors in vivo, with extremely low toxicity. This work provides the proof of concept that ultralong-lived triplet excitons can function as two-photon-activated photosensitizers for an effective singlet oxygen generation.
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