Natural Light Harvesting Research Articles

Probing the Effect of Mutations on Light Harvesting in CP29 by Transient Absorption and First-Principles Simulations.

Natural light harvesting is exceptionally efficient thanks to the local energy funnel created within light-harvesting complexes (LHCs). To understand the design principles underlying energy transport in LHCs, ultrafast spectroscopy is often complemented by mutational studies that introduce perturbations into the excitonic structure of the natural complexes. However, such studies may fall short of identifying all excitation energy transfer (EET) pathways and their changes upon mutation. Here, we show that a synergistic combination of first-principles calculations and ultrafast spectroscopy can give unprecedented insight into the EET pathways occurring within LHCs. We measured the transient absorption spectra of the minor CP29 complex of plants and of two mutants, systematically mapping the kinetic components seen in experiments to the simulated exciton dynamics. With our combined strategy, we show that EET in CP29 is surprisingly robust to the changes in the exciton states induced by mutations, explaining the versatility of plant LHCs.

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.

Synergetic impact of natural light harvesting materials to reduce the recombination rate and improve the device performance of dye sensitized solar cells

Synergetic impact of natural light harvesting materials to reduce the recombination rate and improve the device performance of dye sensitized solar cells

Photo-responsive Porphyrin-protein microfibers with Bacteria-triggered drug release for Synergetic sterilization

The emergence of drug-resistant bacteria (DRB) has been a prominent public healthy challenge caused by the overuse of antibiotics. In nature, protein combines with photosensitizer via non-covalent bond forming photo-system for plant protection. Imitation of natural light harvesting system will be efficient materials for sterilization. Here, a photo-responsive microfiber (PCA@BSA) was constructed by the self-assembly of bovine serum albumin (BSA) with the NH2-NH-CO– groups conjugated porphyrin (P) and caffeic acid (CA, a kind of polyphenol). The surface decoration of gold nanoparticles provided the microfibers (PCA@BSA-Au MFs) with photothermal ability and intensive affinity with bacteria. Biological evaluation unveiled excellent photo-driven (808 nm and red LED) antibacterial efficiency. Particularly, CA encapsulated in PCA@BSA-Au MFs could be released by the trigger of acidic environment or active bacteria, resulting in the enhancement of antibacterial effect and a tenuous morphology of PCA@BSA-Au MFs. These results validate the assembly of porphyrin and natural polyphenols templated protein is a novel photosystem toward antisepsis.

Unequal Perylene Diimide Twins in a Quadruple Assembly.

Natural light-harvesting (LH) systems can divide identical dyes into unequal aggregate states, thereby achieving intelligent "allocation of labor". From a synthetic point of view, the construction of such kinds of unequal and integrated systems without the help of proteinaceous scaffolding is challenging. Here, we show that four octatetrayne-bridged ortho-perylene diimide (PDI) dyads (POPs) self-assemble into a quadruple assembly (POP)4 both in solution and in the solid state. The two identical PDI units in each POP are compartmentalized into weakly coupled PDIs (P520) and closely stacked PDIs (P550) in (POP)4 . The two extreme pools of PDI chromophores were unambiguously confirmed by single-crystal X-ray crystallography and NMR spectroscopy. To interpret the formation of the discrete quadruple assembly, we also developed a two-step cooperative model. Quantum-chemical calculations indicate the existence of multiple couplings within and across P520 and P550, which can satisfactorily describe the photophysical properties of the unequal quadruple assembly. This finding is expected to help advance the rational design of dye stacks to emulate functions of natural LH systems.

Quantum coherent energy transport in the Fenna–Matthews–Olson complex at low temperature

In the primary step of natural light harvesting, the solar photon energy is captured in a photoexcited electron-hole pair, or an exciton, in chlorophyll. Its conversion to chemical potential occurs in the special pair reaction center, which is reached by downhill ultrafast excited-state energy transport through a network of chromophores. Being inherently quantum, transport could in principle occur via a matter wave, with vast implications for efficiency. How long a matter wave remains coherent is determined by the intensity by which the exciton is disturbed by the noisy biological environment. The stronger this is, the stronger the electronic coupling between chromophores must be to overcome the fluctuations and phase shifts. The current consensus is that under physiological conditions, quantum coherence vanishes on the 10-fs time scale, rendering it irrelevant for the observed picosecond transfer. Yet, at low-enough temperature, quantum coherence should in principle be present. Here, we reveal the onset of longer-lived electronic coherence at extremely low temperatures of ∼20 K. Using two-dimensional electronic spectroscopy, we determine the exciton coherence times in the Fenna-Matthew-Olson complex over an extensive temperature range. At 20 K, coherence persists out to 200 fs (close to the antenna) and marginally up to 500 fs at the reaction center. It decays markedly faster with modest increases in temperature to become irrelevant above 150 K. At low temperature, the fragile electronic coherence can be separated from the robust vibrational coherence, using a rigorous theoretical analysis. We believe that by this generic principle, light harvesting becomes robust against otherwise fragile quantum effects.

Steering the multiexciton generation in slip-stacked perylene dye array via exciton coupling

Dye arrays from dimers up to larger oligomers constitute the functional units of natural light harvesting systems as well as organic photonic and photovoltaic materials. Whilst in the past decades many photophysical studies were devoted to molecular dimers for deriving structure-property relationship to unravel the design principles for ideal optoelectronic materials, they fail to accomplish the subsequent processes of charge carrier generation or the detachment of two triplet species in singlet fission (SF). Here, we present a slip-stacked perylene bisimide trimer, which constitutes a bridge between hitherto studied dimer and solid-state materials, to investigate SF mechanisms. This work showcases multiple pathways towards the multiexciton state through direct or excimer-mediated mechanisms by depending upon interchromophoric interaction. These results suggest the comprehensive role of the exciton coupling, exciton delocalization, and excimer state to facilitate the SF process. In this regard, our observations expand the fundamental understanding the structure-property relationship in dye arrays.

A bioinspired sequential energy transfer system constructed via supramolecular copolymerization

Sequential energy transfer is ubiquitous in natural light harvesting systems to make full use of solar energy. Although various artificial systems have been developed with the biomimetic sequential energy transfer character, most of them exhibit the overall energy transfer efficiency lower than 70% due to the disordered organization of donor/acceptor chromophores. Herein a sequential energy transfer system is constructed via supramolecular copolymerization of σ-platinated (hetero)acenes, by taking inspiration from the natural light harvesting of green photosynthetic bacteria. The absorption and emission transitions of the three designed σ-platinated (hetero)acenes range from visible to NIR region through structural variation. Structural similarity of these monomers faciliates supramolecular copolymerization in apolar media via the nucleation-elongation mechanism. The resulting supramolecular copolymers display long diffusion length of excitation energy (> 200 donor units) and high exciton migration rates (~1014 L mol−1 s−1), leading to an overall sequential energy transfer efficiency of 87.4% for the ternary copolymers. The superior properties originate from the dense packing of σ-platinated (hetero)acene monomers in supramolecular copolymers, mimicking the aggregation mode of bacteriochlorophyll pigments in green photosynthetic bacteria. Overall, directional supramolecular copolymerization of donor/acceptor chromophores with high energy transfer efficiency would provide new avenues toward artificial photosynthesis applications.

A fast method for electronic couplings in embedded multichromophoric systems

Electronic couplings are key to understanding exciton delocalization and transport in natural and artificial light harvesting processes. We develop a method to compute couplings in multichromophoric aggregates embedded in complex environments without running expensive quantum chemical calculations. We use a transition charge approximation to represent the quantum mechanical transition densities of the chromophores and an atomistic and polarizable classical model to describe the environment atoms. We extend our framework to estimate transition charges directly from the chromophore geometry, i.e., bypassing completely the quantum mechanical calculations using a regression approach. The method allows to rapidly compute accurate couplings for a large number of geometries along molecular dynamics trajectories.

Efficient nano-photonic antennas based on dark states in quantum emitter rings.

Nanoscopic arrays of quantum emitters can feature highly sub-radiant collective excitations with a lifetime exponentially growing with emitter number. Adding an absorptive impurity as an energy dump in the center of a ring shaped polygon allows to exploit this feature to create highly efficient single photon antennas. Here among regular polygons with an identical center absorbing emitter, a nonagon exhibits a distinct optimum of the absorption efficiency. This special enhancement originates from the unique emergence of a subradiant eigenstate with dominant center occupation. Only for nine emitters the sum of coupling strengths of each emitter to all others matches the center to the ring coupling. Analogous to a parabolic mirror the antenna ring then concentrates incoming radiation at its center without being significantly excited itself. Similar large efficiency enhancements, which even prevail for broadband excitation, can also be engineered for other antenna sizes by tailoring the frequency and magnitude of the central absorber. Interestingly, for very small structures a quantum treatment predicts an even stronger enhancement for the single photon absorption enhancement than a classical dipole model. As natural light harvesting structures are often based on ring shaped structures, the underlying principle might be exploited there as well.

Correlated spectral fluctuations quantified by line shape analysis of fifth-order two-dimensional electronic spectra.

Correlated spectral fluctuations were suggested to coordinate excitation transport inside natural light harvesting complexes. We demonstrate the capacities of 2D line shapes from fifth-order coherent electronic signals (R5-2D) to report on such fluctuations in molecular aggregates and present a stochastic approach to fluctuations in correlated site and bi-exciton binding energies in the optical dynamics of Frenkel excitons. The model is applied to R5-2D line shapes of a homodimer, and we show that the peak tilt dynamics are a measure for site energy disorder, inter-site correlation, and the strength of bi-exciton binding energy fluctuations.

Electronic energy transfer in single conjugated polymer molecules revealed by phase-modulated pulse-pair controlled single molecule spectroscopy

Detailed understanding of the electronic energy transfer dynamics in conjugated polymer molecules and their conformation dependence is central for improving the photophysical properties as well as the performance of devices based on conjugated polymers. In this work, we demonstrate simultaneous measurement of the absorption and emission sites in single conjugated polymer poly[2,7-(9,9-dioctyluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PFO-DBT) molecules based on polarization-resolved confocal fluorescence microscopy with excitation of phase-modulated ultrashort pulse pairs. The evolution of absorbing chromophores can be derived by modulating the relative phase between ultrashort pulse pairs and extracting modulation information in phase-dependent fluorescence. Meanwhile, the emitting chromophore can be measured by polarization-resolved emission. Simultaneous absorption and emission measurements give new insights into the evolution of energy transfer pathways in individual conjugated polymer molecules. The results suggest that the conformation of single conjugated polymer chains can be influenced by solvents. Single PFO-DBT conjugated molecules spin-cast from toluene solution have relatively fixed absorption and emission dipole moments. In contrast, single conjugated polymer molecules prepared with chloroform show multichromophore behavior that is responsible for distribution of absorption and emission in a single chain. The proposed scheme paves the way for further understanding of conformation dependent photophysical properties and the possible role of quantum effects in the energy transfer pathway in both natural and artificial light harvesting systems in the nanoscale.

A Tunable Multivariate Metal-Organic Framework as a Platform for Designing Photocatalysts.

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO2. Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB2OX3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 molH2 gcat.–1 min–1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10–5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

Rotaxane rings promote oblique packing and extended lifetimes in DNA-templated molecular dye aggregates

Molecular excitons play a central role in natural and artificial light harvesting, organic electronics, and nanoscale computing. The structure and dynamics of molecular excitons, critical to each application, are sensitively governed by molecular packing. Deoxyribonucleic acid (DNA) templating is a powerful approach that enables controlled aggregation via sub-nanometer positioning of molecular dyes. However, finer sub-Angstrom control of dye packing is needed to tailor excitonic properties for specific applications. Here, we show that adding rotaxane rings to squaraine dyes templated with DNA promotes an elusive oblique packing arrangement with highly desirable optical properties. Specifically, dimers of these squaraine:rotaxanes exhibit an absorption spectrum with near-equal intensity excitonically split absorption bands. Theoretical analysis indicates that the transitions are mostly electronic in nature and only have similar intensities over a narrow range of packing angles. Compared with squaraine dimers, squaraine:rotaxane dimers also exhibit extended excited-state lifetimes and less structural heterogeneity. The approach proposed here may be generally useful for optimizing excitonic materials for a variety of applications ranging from solar energy conversion to quantum information science.

Engineering couplings for exciton transport using synthetic DNA scaffolds

Summary Control over excitons enables electronic energy to be harnessed and transported for light harvesting and molecular electronics. Such control requires nanoscale precision over the molecular components. Natural light-harvesting systems achieve this precision through sophisticated protein machinery, which is challenging to replicate synthetically. Here, we introduce a DNA-based platform that spatially organizes cyanine chromophores to construct tunable excitonic systems. We synthesized DNA-chromophore nanostructures and characterized them with ensemble ultrafast and single-molecule spectroscopy and structure-based modeling. This synthetic approach facilitated independent control over the coupling among the chromophores and between the chromophores and the environment. We demonstrated that the coupling between the chromophores and the environment could enhance exciton transport efficiency, highlighting the key role of the environment in driving exciton dynamics. Control over excitons, as reported here, offers a path toward the development of designer nanophotonic devices.

Unravelling the Role of Water in Ultrafast Excited-State Relaxation Dynamics within Nano-Architectures of Chlorophyll a.

Water plays a pivotal role in structural stability of supramolecular pigment assemblies designed for natural light harvesting (for example, chlorosome antenna complex) as well as their artificial analogs. However, the dynamic role of water in the context of excite-state relaxation has not been explored till date, which we report here. Using femtosecond transient absorption spectroscopy, we investigate the excited-state dynamics of two types of nano-scale assemblies of chlorophyll a with different structural motifs, rod-shaped and micellar assemblies, that depend on the water content. We show how water participates in excess energy dissipation by vibrational cooling of the non-thermally populated Qy band at different rates in different types of clusters but exhibits no polar solvation dynamics. For the micelles, we observe a bifurcation of stimulated emission line shape, whereas a positive-to-negative switching of differential absorption is observed for the rods; both these observations are correlated with their specific structural aspects. Density functional theory calculations reveal two possible stable ground state geometries of dimers, accounting for the bifurcation of line shape in micelles. Thus, our study elucidates water-mediated structure-function relationship within these pigment assemblies.

Individual tubular J-aggregates stabilized and stiffened by silica encapsulation

Amphiphilic cyanine dyes in aqueous solution self-assemble into J-aggregates with diverse structures. In particular, the dye 3,3′-bis(3-sulfopropyl)-5,5′,6,6′-tetrachloro-1,1′-dioctylbenzimida-carbo-cyanine (C8S3) forms micrometer long double walled tubular J-aggregates with a uniform outer diameter of 13 ± 0.5 nm. Interestingly, these J-aggregates exhibit strong exciton delocalization and migration, similar to natural light harvesting systems. However, their structural integrity and hence their optical properties are very sensitive to their chemical environment as well as to mechanical deformation, rendering detailed studies on individual tubular J-aggregates difficult. We addressed this issue and examined a previously published route for their chemical and mechanical stabilization by in situ synthesis of a silica coating that leaves their absorbance and emission unaltered in solution. Here, we demonstrate that the silica shell with a thickness of a few nanometers is able to stabilize the tubular J-aggregates of C8S3 against changes of pH of solutions down to values where pure aggregates are oxidized, against drying under ambient conditions, and even against the vacuum conditions within an electron microscope. Dried silica–covered aggregates are brittle, as demonstrated by manipulation with a scanning force microscope on a surface. Transmission electron microscope images confirm that the thickness of the coatings is homogeneous and uniform with a thickness of less than 5 nm; scanning TEM energy dispersive X-ray spectroscopy confirms the chemical composition of the shell as SiO2; and electron energy loss spectra could be recorded across a single freely suspended aggregate. Such a silica shell may not only serve for stabilization but also could be the base for further functionalization of the aggregates by either chemical attachment of other units on top of the shell or by inclusion during the synthesis.

Hierarchical Assembly of Peptoid‐Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution

AbstractHerein we show that by appending bulky β‐cyclodextrin (CD) groups onto sheet‐forming peptoids, we obtain cylindrical micelles that further assembly into membranes and intertwined ribbons on substrates in aqueous solution, depending on the choice of solution and substrate conditions. In situ atomic force microscopy (AFM) shows that micelle assembly occurs in two steps, starting with “precursor” particles that transform into worm‐like micelles, which extend and coalesce to form the higher order structures with a rate and a degree of cooperativity dependent on pH and Ca2+ concentration. After co‐assembly with hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole (NBD) donors that occupy the hydrophobic core, followed by exposure to hydrophilic Rhodamine B as acceptors that insert into cyclodextrin, the micelles exhibit highly efficient Förster resonance energy transfer efficiency in aqueous solution, thereby mimicking natural light harvesting systems.

Hierarchical Assembly of Peptoid-Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution.

Herein we show that by appending bulky β-cyclodextrin (CD) groups onto sheet-forming peptoids, we obtain cylindrical micelles that further assembly into membranes and intertwined ribbons on substrates in aqueous solution, depending on the choice of solution and substrate conditions. In situ atomic force microscopy (AFM) shows that micelle assembly occurs in two steps, starting with "precursor" particles that transform into worm-like micelles, which extend and coalesce to form the higher order structures with a rate and a degree of cooperativity dependent on pH and Ca2+ concentration. After co-assembly with hydrophobic 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole (NBD) donors that occupy the hydrophobic core, followed by exposure to hydrophilic Rhodamine B as acceptors that insert into cyclodextrin, the micelles exhibit highly efficient Förster resonance energy transfer efficiency in aqueous solution, thereby mimicking natural light harvesting systems.

Quantum coherences reveal excited-state dynamics in biophysical systems

Ultrafast, multi-dimensional spectroscopic measurements of photosynthetic light-harvesting complexes have revealed quantum coherences with timescales comparable to those of energy-transfer processes. These observations have led to a debate regarding the states that give rise to the coherences and whether the presence of the coherences has implications for photosynthetic light harvesting. In these experiments, laser pulses create a coherent superposition of quantum states with a defined phase relationship across an ensemble, which gives rise to the quantum coherence and associated quantum beating signal. Dephasing of these quantum coherences, seen as a decay of the beating signal, is among the most sensitive probes of the interactions between a system and its surrounding environment. In this Review, we discuss the proposed origin and assignment of the observed quantum coherences in photosynthetic systems as electronic, vibronic or vibrational. We describe the latest experimental efforts towards unravelling the nature of the coherences, in particular ultrafast, two-dimensional electronic spectroscopy, as well as the accompanying theoretical and computational results. We discuss how measuring coherences can inform us about the excited-state dynamics of biophysical and chemical systems relevant to natural light harvesting and how these measurements reveal electronic structure beyond that captured by simplistic models. Femtosecond spectroscopy of photosynthetic systems reveals long-lived quantum coherences. This Review focuses on efforts to understand the microscopic origins of these signals and discusses how such coherences may be exploited to probe design principles of photosynthetic light harvesting.