Light Harvesting and White‐Light Generation in a Composite of Carbon Dots and Dye‐Encapsulated BSA‐Protein‐Capped Gold Nanoclusters

Several strategies have been adopted to design an artificial light‐harvesting system in which light energy is captured by peripheral chromophores and it is subsequently transferred to the core via energy transfer. A composite of carbon dots and dye‐encapsulated BSA‐protein‐capped gold nanoclusters (AuNCs) has been developed for efficient light harvesting and white light generation. Carbon dots (C‐dots) act as donor and AuNCs capped with BSA protein act as acceptor. Analysis reveals that energy transfer increases from 63 % to 83 % in presence of coumarin dye (C153), which enhances the cascade energy transfer from carbon dots to AuNCs. Bright white light emission with a quantum yield of 19 % under the 375 nm excitation wavelength is achieved by changing the ratio of components. Interesting findings reveal that the efficient energy transfer in carbon‐dot–metal‐cluster nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications.     

Efficient Excitation‐Energy Transfer in Ion‐Based Organic Nanoparticles with Versatile Tunability of the Fluorescence Colours

Organic nanoparticles consisting of 3,3′‐diethylthiacyanine (TC) and ethidium (ETD) dyes are synthesized by ion‐association between the cationic dye mixture (10 % ETD doping) and the tetrakis(4‐fluorophenyl)borate (TFPB) anion, in the presence of a neutral stabilizing polymer, in aqueous solution. Doping with ETD makes the particle size smaller than without doping. Size tuning can also be conducted by varying the molar ratio (ρ) of the loaded anion to the cationic dyes. The fluorescence spectrum of TC shows good overlap with the absorption of ETD in the 450–600 nm wavelength region, so efficient excitation‐energy transfer from TC (donor) to ETD (acceptor) is observed, yielding organic nanoparticles whose fluorescence colours are tunable. Upon ETD doping, the emission colour changes significantly from greenish‐blue to reddish or whitish. This change is mainly dependent on ρ. For the doped nanoparticle sample with ρ=1, the intensity of fluorescence ascribed to ETD is ～150‐fold higher than that from pure ETD nanoparticles (efficient antenna effect). Non‐radiative Förster resonance‐energy transfer (FRET) is the dominant mechanism for the ETD fluorescence enhancement. The organic nanoparticles of a binary dye system fabricated by the ion‐association method act as efficient light‐harvesting antennae, which are capable of transferring light energy to the dopant acceptors in very close proximity to the donors, and can have multi‐wavelength emission colours with high fluorescence quantum yields.     

High‐Yield Excited Triplet States in Pentacene Self‐Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission

One of the major drawbacks of organic‐dye‐modified self‐assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13‐bis(triisopropylsilylethynyl)pentacene–alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time‐resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface.     

Integrating DNA Photonic Wires into Light‐Harvesting Supramolecular Polymers

An approach combining DNA nanoscaffolds with supramolecular polymers for the efficient and directional propagation of light‐harvesting cascades has been developed. A series of photonic wires with different arrangements of fluorophores in DNA‐organized nanostructures were linked to light‐harvesting supramolecular phenanthrene polymers (SPs) in a self‐assembled fashion. Among them, a light‐harvesting complex (LHC) composed of SPs and a photonic wire of phenanthrene, Cy3, Cy5, and Cy5.5 chromophores reveals a remarkable energy transfer efficiency of 59 %. Stepwise transfer of the excitation energy collected by the light‐harvesting SPs via the intermediate Cy3 and Cy5 chromophores to the final Cy5.5 acceptor proceeds through a Förster resonance energy transfer mechanism. In addition, the light‐harvesting properties are documented by antenna effects ranging from 1.4 up to 23 for different LHCs.     

Highly Efficient Artificial Light‐Harvesting Systems Constructed in Aqueous Solution Based on Supramolecular Self‐Assembly

Highly efficient light‐harvesting systems were successfully fabricated in aqueous solution based on the supramolecular self‐assembly of a water‐soluble pillar[6]arene (WP6), a salicylaldehyde azine derivative (G), and two different fluorescence dyes, Nile Red (NiR) or Eosin Y (ESY). The WP6‐G supramolecular assembly exhibits remarkably improved aggregation‐induced emission enhancement and acts as a donor for the artificial light‐harvesting system, and NiR or ESY, which are loaded within the WP6‐G assembly, act as acceptors. An efficient energy‐transfer process takes place from the WP6‐G assembly not only to NiR but also to ESY for these two different systems. Furthermore, both of the WP6‐G‐NiR and WP6‐G‐ESY systems show an ultrahigh antenna effect at a high donor/acceptor ratio.     

Playing with dye molecules at the inner and outer surface of zeolite L

Plants are masters of transforming sunlight into chemical energy. In the ingenious antenna system of the leaf, the energy of the sunlight is transported by chlorophyll molecules for the purpose of energy transformation. We have succeeded in reproducing a similar light transport in an artificial system on a nano scale. In this artificial system, zeolite L cylinders adopt the antenna function. The light transport is made possible by specifically organized dye molecules, which mimic the natural function of chlorophyll. Zeolites are crystalline materials with different cavity structures. Some of them occur in nature as a component of the soil. We are using zeolite L crystals of cylindrical morphology which consist of a continuous one-dimensional tube system and we have succeeded in filling each individual tube with chains of joined but noninteracting dye molecules. Light shining on the cylinder is first absorbed and the energy is then transported by the dye molecules inside the tubes to the cylinder ends. We expect that our system can contribute to a better understanding of the important light harvesting process which plants use for the photochemical transformation and storage of solar energy. We have synthesized nanocrystalline zeolite L cylinders ranging in length from 300 to 3000 nm. A cylinder of 800 nm diameter, e.g. consists of about 150 000 parallel tubes. Single red emitting dye molecules (oxonine) were put at each end of the tubes filled with a green emitting dye (pyronine). This arrangement made the experimental proof of efficient light transport possible. Light of appropriate wavelength shining on the cylinder is only absorbed by the pyronine and the energy moves along these molecules until it reaches the oxonine. The oxonine absorbs the energy by a radiationless energy transfer process, but it is not able to send it back to the pyronine. Instead it emits the energy in the form of red light. The artificial light harvesting system makes it possible to realize a device in which different dye molecules inside the tubes are arranged in such a way that the whole visible spectrum can be used by conducting light from blue to green to red without significant loss. Such a material could conceivably be used in a dye laser of extremely small size. The light harvesting nanocrystals are also investigated as probes in near-field microscopy, as materials for new imaging techniques and as luminescent probes in biological systems. The extremely fast energy migration, the pronounced anisotropy, the geometrical constraints and the high concentration of monomers which can be realized, have great potential in leading to new photophysical phenomena. Attempts are being made to use the efficient zeolite-based light harvesting system for the development of a new type of thin-layer solar cell in which the absorption of light and the creation of an electron-hole pair are spatially separated as in the natural antenna system of green plants. Synthesis, characterization and applications of an artificial antenna for light harvesting within a certain volume and transport of the electronic excitation energy to a specific place of molecular dimension has been the target of research in many laboratories in which different approaches have been followed. To our knowledge, the system developed by us is the first artificial antenna which works well enough to deserve this name. Many other highly organized dye–zeolite materials of this type can be prepared by similar methods and are expected to show a wide variety of remarkable properties. The largely improved chemical and photochemical stability of dye molecules inserted in an appropriate zeolite framework allows us to work with dyes which otherwise would be considered uninteresting because of their lack of stability. We have developed two methods for preparing well-defined dye–zeolite materials, one of them working at the solid–liquid and the other at the solid–gas interface. Different approaches for preparing similar materials are in situ synthesis (ship in a bottle) or different types of crystallization inclusion synthesis.     

G‐Quartet‐Based Nanostructure for Mimicking Light‐Harvesting Antenna

Artificial light‐harvesting systems have received great attention for use in photosynthetic and optoelectronic devices. Herein, a system involving G‐quartet‐based hierarchical nanofibers generated from the self‐assembly of guanosine 5′‐monophosphate (GMP) and a two‐step Förster resonance energy transfer (FRET) is presented that mimics natural light‐harvesting antenna. This solid‐state property offers advantages for future device fabrication. The generation of photocurrent under visible light shows it has potential for use as a nanoscale photoelectric device. The work will be beneficial for the development of light‐harvesting systems by the self‐assembly of supramolecular nanostructures.     

A Supramolecular Artificial Light‐Harvesting System with Two‐Step Sequential Energy Transfer for Photochemical Catalysis

An artificial light‐harvesting system with sequential energy‐transfer process was fabricated based on a supramolecular strategy. Self‐assembled from the host–guest complex formed by water‐soluble pillar[5]arene (WP5), a bola‐type tetraphenylethylene‐functionalized dialkyl ammonium derivative (TPEDA), and two fluorescent dyes, Eosin Y (ESY) and Nile Red (NiR), the supramolecular vesicles achieve efficient energy transfer from the AIE guest TPEDA to ESY. ESY can function as a relay to further transfer the energy to the second acceptor NiR and realize a two‐step sequential energy‐transfer process with good efficiency. By tuning the donor/acceptor ratio, bright white light emission can be successfully achieved with a CIE coordinate of (0.33, 0.33). To better mimic natural photosynthesis and make full use of the harvested energy, the WP5?TPEDA‐ESY‐NiR system can be utilized as a nanoreactor: photocatalyzed dehalogenation of α‐bromoacetophenone was realized with 96 % yield in aqueous medium.     

A Complex Comprising a Cyanine Dye Rotaxane and a Porphyrin Nanoring as a Model Light‐Harvesting System

A nanoring‐rotaxane supramolecular assembly with a Cy7 cyanine dye (hexamethylindotricarbocyanine) threaded along the axis of the nanoring was synthesized as a model for the energy transfer between the light‐harvesting complex LH1 and the reaction center in purple bacteria photosynthesis. The complex displays efficient energy transfer from the central cyanine dye to the surrounding zinc porphyrin nanoring. We present a theoretical model that reproduces the absorption spectrum of the nanoring and quantifies the excitonic coupling between the nanoring and the central dye, thereby explaining the efficient energy transfer and demonstrating similarity with structurally related natural light‐harvesting systems.     

A Conjugated Polymeric Supramolecular Network with Aggregation‐Induced Emission Enhancement: An Efficient Light‐Harvesting System with an Ultrahigh Antenna Effect

Superior artificial light‐harvesting systems (ALHSs) require exceptional capacity in harvesting light and transferring energy. In this work, we report a novel strategy to build ALHSs with an unprecedented antenna effect (35.9 in solution and 90.4 in solid film). The ALHSs made use of a conjugated polymeric supramolecular network (CPSN), a crosslinked network obtained from the self‐assembly of a pillar[5]arene‐based conjugated polymeric host ( CPH ) and conjugated ditopic guests (Gs). The excellent performance of the CPSN could be attributed to the following factors: 1) The “molecular wire effect” of the conjugated polymeric structure, 2) aggregation‐induced enhanced emission (AEE) moieties in the CPH backbone, and 3) high capacity of donor–acceptor energy transfer, and 4) crosslinked structures triggered by the host–guest binding between Gs and CPH . Moreover, the emission of the CPSN could be tuned by using different Gs or varying the host/guest ratio, thus reaching a 96 % sRGB area.     

Design and synthesis of core and peripherally functionalized with 1,8-naphthalimide units fluorescent PAMAM dendron as light harvesting antenna

This paper reports on the design, synthesis and spectral characteristics of a novel PAMAM dendron (7), core and peripherally functionalized with 1,8-naphthalimide fluorophores. The novel compound 7 was configured as light harvesting antenna where the system surface is functionalized with “donor” dyes (blue emitting 1,8-naphthalimides) that are capable of absorbing light and efficiently transferring the energy to a single “acceptor” dye (yellow-green emitting 1,8-naphthalimide) in the focal point of the dendron. The overlap between the emission of the donor and the absorbance of the acceptor was more than 95%. As a result of the energy transfer, the blue emission intensity of the periphery in the donor–acceptor system was decreased with 93%, while the yellow-green core fluorescence enhancement (λ_ex = 360 nm) of the system was more than 26 times with respect to the fluorescence intensity of the comparative yellow-green emitting 1,8-naphthalimide. This indicates efficient energy transfer between the donor and acceptor dye fragments and that the novel compound 7 would be able to act as a highly efficient light harvesting antenna.     

Cooperative Chirality and Sequential Energy Transfer in a Supramolecular Light‐Harvesting Nanotube

By constructing a supramolecular light‐harvesting chiral nanotube in the aqueous phase, we demonstrate a cooperative energy and chirality transfer. It was found that a cyanostilbene‐appended glutamate compound (CG) self‐assembled into helical nanotubes exhibiting both supramolecular chirality and circularly polarized luminescence (CPL). When two achiral acceptors, ThT and AO, with different energy bands were co‐assembled with the nanotube, the CG nanotube could transfer its chirality to both of the acceptors. The excitation energy could be transferred to ThT but only be sequentially transferred to AO. During this process, the CPL ascribed to the acceptor could be sequentially amplified. This work provides a new insight into the understanding the cooperative chirality and energy transfer in a chiral supramolecular system, which is similar to the natural light‐harvesting antennas.     

Ultrafast Relaxation Processes of Conjugated Polymer Nanoparticles in the Presence of Au Nanoparticles

Considering the importance of conjugated polymer nanoparticles, major emphasis has been given for designing and understanding the energy transfer and charge transfer processes of organic‐inorganic hybrids for light harvesting applications. In the present study, we have designed an aqueous solution‐based light harvesting system using conjugated polymer nanoparticles (poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene], MEH‐PPV) and Au nanoparticles. The change in photo‐induced processes in the presence of metal nanoparticles are studied by steady‐state absorption, time‐resolved emission, time‐resolved fluorescence up‐conversion, ultrafast anisotropy and femtosecond transient absorption spectroscopy. Global and target analysis of transient absorption data validate the creation of a collective delocalized state in polymer nanoparticles, and the time scale for excitation energy funnelling from S₁ state to low lying collective delocalized state (CL_s) is 18 ps. Then, the electron transfer from the CL_s state to Au NP occurs with a time constant of 150 ps. The 815 ps long lived charge transfer (CT) state signifies the charge transfer from the CL_s state of polymer nanoparticles to Au NP. Such basic understanding of relaxation processes in hybrid systems is very important for designing inorganic‐organic hybrid light‐harvesting systems.     

Fluorescent nanoparticles based on a microporous organic polymer network: fabrication and efficient energy transfer to surface-bound dyes

Well-defined nanoparticles composed of a tetraphenylmethane-based microporous polymer network with an average particle diameter of 30-60 nm were fabricated by a miniemulsion polymerization technique. Strong green emission was observed and efficient excitation energy transfer from nanoparticles to surface-bound dye molecules was explored.     

Light‐Harvesting Three‐Chromophore Systems Based on Biphenyl‐Bridged Periodic Mesoporous Organosilica

Three‐chromophore systems with light‐harvesting behavior were prepared, which are based on periodic mesoporous organosilica (PMO) with crystal‐like ordered structure. The organic bridges of biphenyl‐PMO in the pore walls act as donors and two types of dye are incorporated in the one‐dimensional channels. Consecutive two‐step‐Förster resonance energy transfer is observed from the biphenyl moieties to mediators (diethyl‐aminocoumarin or aminoacridone), followed by energy transfer from mediators to acceptors (dibenzothiacarbocyanine, indodicarbocyanine, sulforhodamine G). High energy‐transfer efficiencies ranging from 70 to 80 % are obtained for two‐step‐FRET, indicating that the mesochannel structure with one‐dimensional ordering provides spatial arrangement of chromophore pairs for an efficient direct energy transfer. The emission wavelength can be tuned by a choice of acceptor dye: 477 nm (diethylaminocoumarin), 519 nm (aminoacridone), 567 nm (sulforhodamine G), 630 nm (dibenzothiacarbocyanine), and 692 nm (indodicarbocyanine).     

Hierarchical Self‐Assembly of a Biomimetic Light‐Harvesting Antenna Based on DNA G‐Quadruplexes

A new modular approach to an artificial light‐harvesting antenna system is presented. The approach involves the hierarchical self‐assembly of porphyrin acceptor molecules to G‐quadruplexes tethered to coumarin donor moieties.     

Long‐Distance Electronic Energy Transfer in Light‐Harvesting Supramolecular Polymers

The efficient collection of solar energy relies on the design and construction of well‐organized light‐harvesting systems. Herein we report that supramolecular phenanthrene polymers doped with pyrene are effective collectors of light energy. The linear polymers are formed through the assembly of short amphiphilic oligomers in water. Absorption of light by phenanthrene residues is followed by electronic energy transfer along the polymer over long distances (>100 nm) to the accepting pyrene molecules. The high efficiency of the energy transfer, which is documented by large fluorescence quantum yields, suggests a quantum coherent process.     

Highly Branched Polymers with Layered Structures that Mimic Light‐Harvesting Processes

Hyperbranched polymers (HBPs) with decorated donor and acceptor chromophores in different domains were constructed to demonstrate the function of light harvesting in a polymeric nanostructure. Taking advantage of our recently developed chain‐growth copper‐catalyzed azide–alkyne cycloaddition polymerization, two structural parameters in the HBPs, for example, the molar ratio of the acceptor Coumarin 343 in the core to the donor Coumarin 2 on the periphery, and the average distance between these two layers, could be independently varied in a one‐pot synthesis. The results demonstrated an efficient energy transfer from the excited Coumarin 2 to the ground‐state Coumarin 343 in the core, with the efficiency of the energy transfer reaching as high as 98 %. The excited Coumarin 343, after receiving energy from donor Coumarin 2 emitted higher fluorescence intensity than when directly excited, indicating an observed light concentration effect from the periphery dye to the central dye in one polymer structure.     

LASER SPECTROSCOPY OF MODEL PHOTOSYNTHETIC SYSTEMS

Abstract— The goal of the present work was to create and investigate a model system, using a dye imbedded into polymer structure, and to examine characteristics which would provide low heat dissipation and excitation diffusion characteristics approaching those seen in the "antenna" of the photosynthetic apparatus. Zinc tetraphenoxyphtalocyanine served as a dye, and different types of polyvinyl pyridine polymers and polystyrene were used as polymer matricies. Measurements of the absorption, fluorescence and Raman spectra of the polymeric films with dye molecules show that along with Van der Waals interactions of the dye molecules with the side aromatic groups of the polymer there is a coordination interaction between the metal atoms of Zinc phtalocyanine and the nitrogen atoms of the pyridine group of the polymer. A model system shows low heat losses of excitation energy, when the dye concentration does not exceed 10^-2 M (mean distances between molecules of about 34 Å). Electronic excitation diffusion characteristics appeared to be close to those of the light harvesting antenna of the photosynthetic apparatus, indicating high efficiency of the energy migration in it.     

Cyclic Tetramers of Zinc Chlorophylls as a Coupled Light‐Harvesting Antenna–Charge‐Separation System

A coupled light‐harvesting antenna–charge‐separation system, consisting of self‐assembled zinc chlorophyll derivatives that incorporate an electron‐accepting unit, is reported. The cyclic tetramers that incorporated an electron acceptor were constructed by the co‐assembly of a pyridine‐appended zinc chlorophyll derivative, ZnPy , and a zinc chlorophyll derivative further decorated with a fullerene unit, ZnPyC₆₀ . Comprehensive steady‐state and time‐resolved spectroscopic studies were conducted for the individual tetramers of ZnPy and ZnPyC₆₀ as well as their co‐tetramers. Intra‐assembly singlet energy transfer was confirmed by singlet–singlet annihilation in the ZnPy tetramer. Electron transfer from the singlet chlorin unit to the fullerene unit was clearly demonstrated by the transient absorption of the fullerene radical anion in the ZnPyC₆₀ tetramer. Finally, with the co‐tetramer, a coupled light‐harvesting and charge‐separation system with practically 100 % quantum efficiency was demonstrated.