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.

Construction of artificial light-harvesting systems based on a variety of polyelectrolyte materials and application in photocatalysis.

In the present work, we designed and synthesized a cationic cyano-substituted p-phenylenevinylene derivative (PPTA), which can form supramolecular assemblies through electrostatic interaction with a type of polyelectrolyte material anionic guar gum (GP5A). A polyelectrolyte-based artificial light-harvesting system (LHS) was constructed by selecting a fluorescent dye sulforhodamine 101 (SR101) that matched its energy level as an energy acceptor. The energy harvested by the acceptors was used in the aqueous phase cross dehydrogenation coupling (CDC) reaction with a yield of up to 87%. In addition, the general applicability of polyelectrolyte materials to build artificial LHS was demonstrated by three other polyelectrolyte materials sodium polyphenylene sulfonate (RSS), sodium carboxymethyl cellulose (CMC), and sodium polyacrylate (PAAS), in which the CDC reaction was also carried out by these three LHSs and obtained high yields. This work not only provides a new method to construct LHSs by using polyelectrolyte materials, but also provides a beneficial exploration for further applying the energy harvested in LHSs to the field of photocatalysis in an aqueous solution.

Amphiphilicity-Controlled Polychromatic Emissive Supramolecular Self-Assemblies for Highly Sensitive and Efficient Artificial Light-Harvesting Systems.

Dynamic sequential control of photoluminescence by supramolecular approaches has become a great issue in supramolecular chemistry. However, developing a systematic strategy to construct polychromatic photoluminescent supramolecular self-assemblies for improving the efficiency and sensitivity of artificial light-harvesting systems still remains a challenge. Here, a series of amphiphilicity-controlled supramolecular self-assemblies with polychromatic fluorescence based on lower-rim hexyl-modified sulfonatocalix[4]arene (SC4A6) and N-alkyl-modified p-phenylene divinylpyridiniums (PVPn, n = 2-7) as efficient light-harvesting platforms is reported. PVPn shows wide ranges of polychromatic fluorescence by co-assembling with SC4A6, whose emission trends significantly depend on the modified alkyl-chains of PVPn. The formed PVPn-SC4A6 co-assemblies as light-harvesting platforms are extremely sensitive for transferring the energy to two near-infrared emissive acceptors, Nile blue (NiB) and Rhodamine 800. After optimizing the amphiphilicity of PVPn-SC4A6 systems, the PVPn-SC4A6-NiB light-harvesting systems achieve an ultrasensitive working concentration for NiB (2 nm) and an ultrahigh antenna effect up to 91.0. Furthermore, the two different kinds of light-harvesting nanoparticles exhibit good performance on near-infrared imaging in the Golgi apparatus and mitochondria, respectively.

Optimal Energy Transfer in Light-Harvesting Systems.

Photosynthesis is one of the most essential biological processes in which specialized pigment-protein complexes absorb solar photons, and with a remarkably high efficiency, guide the photo-induced excitation energy toward the reaction center to subsequently trigger its conversion to chemical energy. In this work, we review the principles of optimal energy transfer in various natural and artificial light harvesting systems. We begin by presenting the guiding principles for optimizing the energy transfer efficiency in systems connected to dissipative environments, with particular attention paid to the potential role of quantum coherence in light harvesting systems. We will comment briefly on photo-protective mechanisms in natural systems that ensure optimal functionality under varying ambient conditions. For completeness, we will also present an overview of the charge separation and electron transfer pathways in reaction centers. Finally, recent theoretical and experimental progress on excitation energy transfer, charge separation, and charge transport in artificial light harvesting systems is delineated, with organic solar cells taken as prime examples.