ABSTRACT
Ultraviolet (UV, λ<400â nm) light is essential for various photochemical reactions, but its intensity in the solar spectrum is very low, and light sources that artificially generate high-energy UV light are inefficient and environmentally unfriendly. A solution to this problem is photon upconversion (UC) from visible (vis, λ>400â nm) light to UV light. Among several mechanisms, UC based on triplet-triplet annihilation (TTA-UC) in particular has made remarkable progress in recent years. The development of new chromophores has enabled highly efficient conversion of low-intensity visible light into UV light. In this review, we summarize the recent development of visible-to-UV TTA-UC, from the development of chromophores and their production into films to their application in various photochemical processes such as catalysis, bond activation and polymerization. Finally, challenges and opportunities in future material development and applications will be discussed.
Subject(s)
Photochemical Processes , Ultraviolet Rays , Catalysis , Photons , PolymerizationABSTRACT
Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable light-to-chemical energy conversion systems.
ABSTRACT
For the practical application of triplet-triplet annihilation-based photon upconversion (TTA-UC), the development of rigid, transparent, air-stable, and moldable materials with a high TTA-UC efficiency remains a challenging issue. In addition to the noncovalent introduction of ionic liquid emitters into the epoxy network, we covalently introduce emitters with polymerization sites to increase the emitter concentration to 35.6 wt %. A TTA-UC quantum yield ΦUC of 5.7% (theoretical maximum: 50%) or a TTA-UC efficiency ηUC of 11.4% (theoretical maximum: 100%) is achieved, which is the highest value ever achieved for a rigid polymer material. More importantly, the high emitter concentration speeds up the triplet diffusion and suppresses the back energy transfer from the emitter to sensitizer so that the sensitized emitter triplet can be effectively utilized for TTA. The generality of our finding is also confirmed for epoxy resins of similar emitter unit concentrations without the ionic liquid. This work provides important design guidelines for achieving highly efficient TTA-UC in rigid solid materials, which has been very difficult to achieve in the past. Furthermore, the solid-state TTA-UC exhibits high air stability, reflecting the high oxygen barrier performance of epoxy resins. The high moldability of epoxy resins allows the construction of upconversion materials with complex geometries at nano- to macroscopic scales.
ABSTRACT
Efficient and long-term stable triplet-triplet annihilation upconversion (TTA-UC) can be achieved by effectively protecting the excited organic triplet ensembles from photoinduced oxygen quenching, and discovery of a new material platform that promotes TTA-UC in ambient conditions is of paramount importance for practical applications. In this study, we present the first demonstration of an organic nonparaffin phase-change material (PCM) as an air-tolerant medium for TTA-UC with a unique solid-liquid phase transition in response to temperature variation. For the proposed concept, 2,4-hexadien-1-ol is used and extensively characterized with several key features, including good solvation capacity, mild melting point (30.5 °C), and exclusive antioxidant property, enabling a high-efficiency, low-threshold, and photostable TTA-UC system without energy-intensive degassing processes. In-depth characterization reveals that the triplet diffusion among the transient species, i.e., 3sensitizer* and 3acceptor*, is efficient and well protected from oxygen quenching in both aerated liquid- and solid-phase 2,4-hexadien-1-ol. We also propose a new strategy for the nanoencapsulation of PCM by employing hollow mesoporous silica nanoparticles as vehicles. This scheme is applicable to both aqueous- and solid-phase TTA-UC systems as well as suitable for various applications, such as thermal energy storage and smart drug delivery.
