Artificial Light-harvesting Systems Research Articles

Enhanced Emission in Polyelectrolyte Assemblies for the Development of Artificial Light-Harvesting Systems and Color-Tunable LED Device.

Artificial light-harvesting systems (LHSs) are of growing interest for their potential in energy capture and conversion, but achieving efficient fluorescence in aqueous environments remains challenging. In this study, a novel tetraphenylethylene (TPE) derivative, TPEN, is synthesized and co-assembled with poly(sodium 4-styrenesulfonate) (PSS) to enhance its fluorescence via electrostatic interactions. The resulting PSS⊃TPEN network significantly increased blue emission, which is further harnessed by an energy-matched dye, 4,7-di(2-thienyl)benzo[2,1,3]thiadiazole (DBT), to produce an efficient LHS with yellow emission. Moreover, this system is successfully applied to develop color-tunable light-emitting diode (LED) devices. The findings demonstrate a cost-effective and environmentally friendly approach to designing tunable luminescent materials, with promising potential for future advancements in energy-efficient lighting technologies.

Artificial Light-Harvesting Systems with a Three-Step Sequential Energy Transfer Mechanism for Efficient Photocatalytic Minisci-Type Late-Stage Functionalization.

The natural process of photosynthesis involves a series of consecutive energy transfers, but achieving more steps of efficient energy transfer and photocatalytic organic conversion in artificial light-harvesting systems (ALHSs) continues to pose a significant challenge. In the present investigation, a range of ALHSs showcasing a sophisticated three-step energy transfer mechanism is designed, which are meticulously crafted using pillar[5]arene (WP[5]) and p-phenylenevinylene derivative (PPTPy), utilizing host-guest interactions as energy donors. Three distinct types of fluorescent dyes, namely Rhodamine B (RhB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5), are employed as acceptors of energy. Starting from PPTPy-2WP[5], energy is sequentially transferred to RhB, SR101, and Cy5, successfully constructing a multi-step continuous energy transfer system with high energy transfer efficiency. More interestingly, as energy is progressively transferred, the efficiency of superoxide anion radical (O2 •-) generation gradually increased, while the efficiency of singlet oxygen (1O2) generation decreased, achieving the transformation from type II photosensitizer to type I photosensitizer. Furthermore, in order to fully utilize the energy harvested and reactive oxygen species (ROS) obtained, the ALHSs employ a multi-step sequential energy transfer process to enhance Minisci-type alkylation reactions with aldehydes through photocatalysis for late-stage functionalization in an aqueous environment, achieving a 91% yield.

Artificial light-harvesting system with sequential energy transfer in photocatalytic C[sbnd]P coupling based on supramolecular organic framework of triphenylamine

Porous structures exhibit an increased access surface area, thereby promoting the efficient transportation of active oxygen species. Reinforcing the development of artificial light-harvesting systems (LHSs) with porous structured supramolecular organic frameworks (SOFs) as the energy donor can significantly enhance its photocatalytic performance, thereby facilitating efficient organic transformation via photocatalysis. In this investigation, we have successfully fabricated a supramolecular organic framework (MT-SOF) composed of cucurbit[8]uril (CB[8]) and triphenylamine derivative (MeTPPA). Because of the framework structure and large ring restriction in MT-SOF, its fluorescence emission shows a significant increase when compared to that of the individual MeTPPA molecule. By harnessing the remarkable fluorescence emission characteristics of MT-SOF, it was employed as an energy donor in conjunction with Sulforhodamine 101 (SR101) and Cyanine 5 (Cy5) as acceptors to fabricate sequential energy transfer LHS. MT-SOF-SR101-Cy5 has the ability to act as a photosensitizer, facilitating the CP bond coupling with broad applicability. It is important to mention that when compared to MeTPPA, MT-SOF and MT-SOF-SR101, the photocatalytic performance of MT-SOF-SR101-Cy5, featuring continuous two-step energy transfer, shows significant improvement, which can be attributed to the porous structure of MT-SOF and the increased efficiency in generating superoxide anion radical (O2−)

Discrete Macrocyclic Polymer Hosts-Induced Cascade Luminescence Enhancement and Application in Bioimaging.

The integration of polymers, supramolecular macrocycles and aggregation-induced emission (AIE) molecules provides numerous possibilities for constructing various functional supramolecular systems. Herein, we constructed supramolecular assembled systems based on discrete macrocyclic polymer hosts via the cooperation of hydra-headed macrocycles containing two or three pillar[5]arene units (defined as P2, P3), the block polymer F127 and AIE molecules (alkyl-cyano modified tetraphenylethene, alkyl-triazole-cyano modified 9,10-distyrylanthracene, defined as TPE-(CN)4 and DSA-(TACN)2). Compared with the binary assembly between hydra-headed hosts or F127 and AIE molecules, cascaded supramolecular assembly-induced emission enhancement (SAIEE) in aqueous solution was achieved in discrete macrocyclic polymer-based supramolecular assembled systems. Considering the cascaded SAIEE performance, we have successfully applied discrete macrocyclic polymer-based supramolecular assembled systems to bioimaging and constructed an artificial light-harvesting system (LHs) to explore more potential applications. The supramolecular assembly form of discrete macrocyclic polymers hosts and AIE molecules proposed in this work provides new inspiration for the construction and application of high-performance supramolecular luminescent systems.

An Aggregation-Induced Emissive Platinum(II) Metallacycle as the Energy Donor of Rhodols for Ratiometric Detection of Hydrazine.

Industry-produced hydrazine (N2H4) is released into the environment, posing a major risk to human health and the ecosystem. Therefore, it is imperative to develop an effective and convenient method for the detection of N2H4. Herein, artificial light-harvesting systems (ALHSs) for N2H4 detection were constructed by applying an aggregation-induced emission-active platinum(II) metallacycle (TPEMc) as the energy donor and rhodols (P1, P2, and P3) as the energy acceptors. The ratiometric fluorescence probes based on ALHSs for N2H4 showed obvious signal amplification and lower limits of detection compared to those of rhodols (P1, P2, P3) alone. The TPEMc-rhodols systems clearly demonstrated a noticeable increase in fluorescence intensity at 550 nm and an obvious fluorescent color shift from cyan to yellow in the presence of N2H4. Fascinatingly, N2H4 could be visually and quantitatively detected in water by the TPEMc-rhodol systems paired with smartphone RGB analysis. Therefore, the combination of platinum(II) metallacycle with rhodols is a promising strategy for simple, sensitive, and visual detection of N2H4.

An Artificial Light-Harvesting System based on Supramolecular AIEgen Assembly.

Photosynthesis is a complex multi-step process in which light collection is the initial step of photosynthesis and plays an important role in the utilization of solar energy. In order to improve the utilization of sunlight, researchers have developed a variety of artificial light-harvesting systems to simulate photosynthesis in nature. Here, we report a supramolecular artificial light-harvesting system in aqueous solution. Since β-cyclodextrin (β-CD) has a hydrophobic cavity and a hydrophilic outer surface, we adopt β-cyclodextrin (β-CD) as the host molecule and use adamantane as the guest molecule. At the same time, we modified β-CD with the donor molecule naphthalimide and adamantane with the tetraphenylethylene molecule which has aggregation-induced emission (AIE) effects. By using fluorescent molecules with AIE, the self-quenching effect caused by aggregation in aqueous solution can be effectively avoided. Due to the host-guest interaction of β-CD and adamantane, nanoparticles with stable structure and uniform size can be spontaneously assembled in water. Because of the close distance and strong spectral overlap between naphthalimide and tetraphenylethylene, Förster resonance energy transfer (FRET) was realized, and artificial light-harvesting system was successfully constructed in aqueous solution. Therefore, this study provides a new strategy for constructing artificial light-harvesting system, and the artificial light-harvesting system shows broad application prospects in aqueous solutions.

Host-Guest Approach to Promoting Photocatalysis Based on Consecutive Photo-Induced Electron-Transfer Processes via Efficient Förster Resonance Energy Transfer.

Supramolecular artificial light-harvesting system with highly efficient host-guest energy transfer pathway provides an ideal platform for optimizing the photochemistry process. The consecutive photo-induced electron transfer (conPET) process overcomes the energy limitation of visible-light photocatalysis, but is often compromised by mismatching between the absorption of ground state dye and its radical, weakening the efficiency of photoredox reaction. By encapsulating a conPET photocatalyst rhodamine 6G into metal-organic cage, the supramolecular approach was undertaken to tackle the intrinsic difficulty of matching the light absorption of photoexcitation between rhodamine 6G and its radical. The highly efficient Förster resonance energy transfer from the photoexcited cage to rhodamine 6G forced by host-guest encapsulation facilitates the conPET process for the single-wavelength light-driven activation of aryl halides by stabilizing and accelerating the production and accumulation of the rhodamine 6G radical intermediate. The tunable and flexible nature of the supramolecular host-guest complex renders the cage-based encapsulation strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy.

Multi-Step and Switchable Energy Transfer in Photoluminescent Organosilicone Capsules.

Light-harvesting is of vital importance for many events, such as photosynthesis. To efficiently gather and transfer solar energy, delicate antenna is needed, which has been achieved by algae and plants. However, construction of efficient light-harvesting systems using multiple, artificial building blocks is still challenging. Here, blue-emitting organosilicone capsules containing carbon dots (denoted as CDs-Si) in ethanol are prepared, which can effectively transfer energy to green-emitting (silicone-functionalized bodipy, Si-BODIPY) or red-emitting (rhodamine b, RhB) dyes. In ternary system, sequential Förster resonance energy transfer from CDs-Si to Si-BODIPY and further to RhB is realized, which is accompanied with a less pronounced, parallel FRET directly from CDs-Si to RhB. The overall efficiency of energy transfer reaches ≈86%. By introducing a photoswitch (1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene, DAE) to the system, the emission becomes switchable under alternative illumination with UV and visible light, leading to the formation of smart artificial light-harvesting systems.

Construction of an Artificial Sequential Light-Harvesting System and White-Light Material Utilizing Supramolecular Gels.

The molecular (pyren-1-yloxy)-acetic acid (Py) with excellent fluorescence properties was synthesized from 1-hydroxypyrene (Hp) and formed a supramolecular gel with an acid-base stimulus response in dimethylformamide and water. On the basis of gel, the fluorescent dye perylene 3, 9-dicarbxylic acid, and rhodamine 6g were added successively to construct a step-by-step artificial light-harvesting system, so that the fluorescence color changed from blue-purple to green to red, and white light emission was realized by adjusting the ratio of donors and acceptors.

Comprehensive Study of Artificial Light-Harvesting Systems with a Multi-Step Sequential Energy Transfer Mechanism.

Artificial light-harvesting systems (LHSs) with a multi-step sequential energy transfer mechanism significantly enhance light energy utilization. Nonetheless, most of these systems exhibit an overall energy transfer efficiency below 80%. Moreover, due to challenges in molecularly aligning multiple donor/acceptor chromophores, systems featuring ≥3-step sequential energy transfer are rarely reported. Here, a series of artificial LHSs is introduced featuring up to 4-step energy transfer mechanism, constructed using a cyclic peptide-based supramolecular scaffold. These LHSs showed remarkably high energy transfer efficiencies (≥90%) and satisfactory fluorescence quantum yields (ranging from 17.6% to 58.4%). Furthermore, the structural robustness of the supramolecular scaffold enables a comprehensive study of these systems, elucidating the associated energy transfer pathways, and identifying additional energy transfer processes beyond the targeted sequential energy transfer. Overall, this comprehensive investigation not only enhances the understanding of these LHSs, but also underscores the versatility of cyclic peptide-based supramolecular scaffolds in advancing energy harvesting technologies.

Unraveling Electronic and Vibrational Coherences Following a Charge Transfer Process in a Photosystem II Reaction Center

A reaction center is a unique biological system that performs the initial charge separation within a Photosystem II (PSII) multiunit enzyme, which eventually drives the catalytic water-splitting in plants and algae. The possible role of quantum coherences coinciding with the energy and charge transfer processes in PSII reaction center is one of the active areas of research. Here, we study these quantum coherences by using a numerically exact method on an excitonic dimer model, including linear vibronic coupling and employing optimal parameters from experimental two-dimensional coherent spectroscopic measurements. This enables us to precisely capture the excitonic interaction between pigments and the dissipation of the energy from electronic and charge-transfer (CT) states to the protein environment. We employ the time nonlocal (TNL) quantum master equation to calculate the population dynamics, which yields numerically reliable results. The calculated results show that, due to the strong dissipation, the lifetime of electronic coherence is too short to have direct participation in the charge transfer processes. However, there are long-lived vibrational coherences present in the system at frequencies close to the excitionic energy gap. These are strongly coupled with the electronic coherences, which makes the detection of the electronic coherences with conventional techniques very challenging. Additionally, we unravel the strong excitonic interaction of radical pair (PD1 and PD2) in the reaction center, which results in a long-lived electronic coherence of >100 fs, even at room temperature. Our work provide important physical insight to the charge separation process in PSII reaction center, which may be helpful for better understanding of photophysical processes in other natural and artificial light-harvesting systems.

Hierarchical Self-Assembly of Multidimensional Functional Materials from Sequence-Defined Peptoids.

Hierarchical self-assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular-level understanding of the hierarchical assembly of sequence-defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron-based powder X-ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence-defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Hierarchical Self‐Assembly of Multidimensional Functional Materials from Sequence‐Defined Peptoids

AbstractHierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Alignment of fibrous J-aggregates and the resulting macroscopic optical anisotropy observed in static solution.

J-aggregates, which are supramolecular assemblies that exhibit unique optical properties owing to their excitonic interactions, have potential applications in artificial light-harvesting systems and fluorescence biosensing. Although J-aggregates are formed in solution, in situ observations of their structures and behaviors in solution remain scarce. In this study, we investigated the J-aggregates of 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate [DiIC18(3)] in methanol/water (M/W) binary solvents using fluorescence imaging as well as polarized absorption and fluorescence measurements to explore the relationship between their structure and macroscopic optical properties under static conditions. Fluorescence images revealed that the DiIC18(3) J-aggregates have fibrous structures in the M/W = 44/56 (v/v) binary solvent. We measured the polarization-angle dependence of the fluorescence intensity of the fibrous J-aggregates to determine the direction of their transition dipole moment. Furthermore, the J-band absorbance was dependent on the polarization angle of the linearly polarized incident light, even in the absence of an external force such as that generated by a flow or stirring, indicating that the J-aggregates "spontaneously" aligned in solution. We also monitored the time evolution of the degree of alignment of the fibrous J-aggregates, which revealed that the formation and elongation of the fibers induced their alignment, resulting in the observed macroscopic optical anisotropy in solution.

A novel supramolecular assembly based on nor-seco-cucurbit[10]uril for spermine sensing and artificial light-harvesting

A supramolecular assembly composed of perylene diimide derivative (PDI-nm) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed. The excellent host-guest interaction between PDI-nm and ns-Q[10] prevented the aggregation-caused quenching (ACQ) effect of PDI-nm, resulting in a luminescent assembly. The addition of spermine to the PDI-nm/ns-Q[10] assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10], which released PDI-nm. The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as 7.84 × 10−7 mol/L in aqueous solution and 3.69 × 10−7 mol/L in plasma solution. Moreover, an artificial light-harvesting system based on this assembly was proposed, benefiting from its good luminescent performance. Nile red (NiR) functioned as an acceptor loaded into assembly, and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10] to NiR, with an efficiency up to 87 %.

Pt(II)/Pd(II)-Based Metallosupramolecular Architectures as Light Harvesting Systems and their Applications.

The development of artificial light-harvesting systems mimicking the natural photosynthesis method is an ever-growing field of research. Numerous systems such as polymers, metal complexes, POFs, COFs, supramolecular frameworks etc. have been fabricated to accomplish more efficient energy transfer and storage. Among them, the supramolecular coordination complexes (SCCs) formed by non-covalent metal-ligand interaction, have shown the capacity to not only undergo single and multistep energy migration but also to utilize the harvested energy for a wide variety of applications such as photocatalysis, tunable emissive systems, encrypted anti-counterfeiting materials, white light emitters etc. This review sheds light on the light-harvesting behavior of both the 2D metallacycles and 3D metallacages where design ingenuity has been executed to afford energy harvesting by both donor ligands as well as metal acceptors.

Construction of an Artificial Light-Harvesting System with Photocatalytic Activity Based on Nor-seco-cucurbit[10]uril in Aqueous Solution.

A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor-seco-cucurbit[10]uril (ns-Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ns-Q[10] assembly, an energy transfer process can occur from the TPEs@ns-Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ns-Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ns-Q[10] assembly and an energy transfer process can take place from the TPEs@ns-Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ns-Q[10]-RB-NiR and TPEs@ns-Q[10]-ESY system, we applied the TPEs@ns-Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ns-Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.

Study on Artificial Light‐Harvesting System Based on Polymer Organogels

AbstractHerein, a simple method for developing an artificial light‐harvesting system (ALHS) based on polymer organogels using benzimidazole carboxylic acid derivatives (RJ) is introduced. The prepared polymer organogels (RJZ) exhibited good luminescence and mechanical properties. The involved energy transfer was obtained by employing RJZ as a donor and the dyes Nile red and SR101 as receptors. The findings of this research will aid in advancing the field of ALHSs. Moreover, the prepared ALHS has application potential in the field of agricultural greenhouse light‐transfer films and energy.

Bioinspired polymeric supramolecular columns as efficient yet controllable artificial light-harvesting platform

Light-harvesting is an indispensable process in photosynthesis, and researchers have been exploring various structural scaffolds to create artificial light-harvesting systems. However, achieving high donor/acceptor ratios for efficient energy transfer remains a challenge as excitons need to travel longer diffusion lengths within the donor matrix to reach the acceptor. Here, we report a polymeric supramolecular column-based light-harvesting platform inspired by the natural light-harvesting of purple photosynthetic bacteria to address this issue. The supramolecular column is designed as a discotic columnar liquid crystalline polymer and acts as the donor, with the acceptor intercalated within it. The modular columnar design enables an ultrahigh donor/acceptor ratio of 20000:1 and an antenna effect exceeding 100. Moreover, the spatial confinement within the supramolecular columns facilitates control over the energy transfer process, enabling dynamic full-color tunable emission for information encryption applications with spatiotemporal regulation security.

Construction and Performance Study of Artificial Light‐harvesting Based on Al3+ Fluorescence Regulation

AbstractA light‐emission system coordinating the amide 2‐amino‐3‐5‐dibromo‐N‐((2‐hydroxy‐naphthalene) benzoylhydrazine (R) and Al3+ was successfully prepared. Compared with that of R, the fluorescence emission band of the R–Al3+ group considerably improved. Therefore, using the R–Al3+ complex as a donor and two dyes (Nile Red and SR101) as acceptors, two artificial light–harvesting systems (ALHSs) were prepared. The energy transfer processes of the R–Al3+–Nile Red and R–Al3+–SR101 systems were confirmed. The findings will help in improving the current situation of ALHSs and have potential application value in ion detection and energy development.