Observation of Vibronic-Coupling-Mediated Energy Transfer in Light-Harvesting Nanotubes Stabilized in a Solid-State Matrix

Pandya, Raj; Chen, Richard Y. S.; Cheminal, Alexandre; Thomas, T. H.; Thampi, Arya; Tanoh, Arelo; Richter, Johannes M.; Shivanna, Ravichandran; Deschler, Felix; Schnedermann, Christoph; Rao, Akshay

doi:10.1021/acs.jpclett.8b02325

Cited by 19 publications

(34 citation statements)

References 55 publications

(108 reference statements)

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“…The transfer rate from the outer to the inner tube was measured using conventional 2D spectroscopy (Supplementary Note 13 and Supplementary Fig. 24) and agrees with the values from literature 18,69,70 . The opposite rate (inner → outer) follows from the condition that the inner and outer tube exciton populations eventually reach thermal equilibrium, where the net inter-tube transfer rates are identical 63,64 .…”

Section: Methodssupporting

confidence: 82%

“…Recent studies have focused on reducing the complexity of multi-layered, supramolecular nanotubes and thereby essentially uncoupling individual hierarchical units, i.e., the inner and outer layer of the assembly by oxidation chemistry 7,8,17,18 . In addition, Eisele et al have demonstrated flash-dilution as an elegant tool to selectively dissolve the outer layer to obtain an unobscured view on the isolated inner layer 7,14 .…”

Section: Introductionmentioning

confidence: 99%

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Interplay between structural hierarchy and exciton diffusion in artificial light harvesting

et al. 2019

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Unraveling the nature of energy transport in multi-chromophoric photosynthetic complexes is essential to extract valuable design blueprints for light-harvesting applications. Long-range exciton transport in such systems is facilitated by a combination of delocalized excitation wavefunctions (excitons) and exciton diffusion. The unambiguous identification of the exciton transport is intrinsically challenging due to the system’s sheer complexity. Here we address this challenge by employing a spectroscopic lab-on-a-chip approach: ultrafast coherent two-dimensional spectroscopy and microfluidics working in tandem with theoretical modeling. We show that at low excitation fluences, the outer layer acts as an exciton antenna supplying excitons to the inner tube, while under high excitation fluences the former converts its functionality into an exciton annihilator which depletes the exciton population prior to any exciton transfer. Our findings shed light on the excitonic trajectories across different sub-units of a multi-layered artificial light-harvesting complex and underpin their great potential for directional excitation energy transport.

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Section: Methodssupporting

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Interplay between structural hierarchy and exciton diffusion in artificial light harvesting

et al. 2019

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“…Elsewhere, the rigid scaffold chromophore interactions of natural lightharvesting systems have been mimicked with cyanine dye-derived host solid-state matrix. Focusing on the structural similarities to chromosomal assemblies in green sulfur bacteria capable of low-light photosynthesis, the solid-state environment was found to modulate vibronic coupling of the system and direct energy transfer [192]. Agglomeration of dyes into nanotubes and structured bundles bio-inspired green bacteria facilitated longer exciton diffusion lengths and wider exciton delocalisation consistent with theory [193][194][195].…”

Section: Bio-inspired Synthetic Light Harvesting Systemsmentioning

confidence: 66%

Quantum Biology: An Update and Perspective

et al. 2021

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Understanding the rules of life is one of the most important scientific endeavours and has revolutionised both biology and biotechnology. Remarkable advances in observation techniques allow us to investigate a broad range of complex and dynamic biological processes in which living systems could exploit quantum behaviour to enhance and regulate biological functions. Recent evidence suggests that these non-trivial quantum mechanical effects may play a crucial role in maintaining the non-equilibrium state of biomolecular systems. Quantum biology is the study of such quantum aspects of living systems. In this review, we summarise the latest progress in quantum biology, including the areas of enzyme-catalysed reactions, photosynthesis, spin-dependent reactions, DNA, fluorescent proteins, and ion channels. Many of these results are expected to be fundamental building blocks towards understanding the rules of life.

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“…We prepare the stabilized aggregates using a previously reported sugar matrix stabilization procedure (pictures shown in Figure 3c). 39,52 Comparison of solution and sugar matrix stabilized aggregates (shown in SI Figure S8a) strongly suggests that the aggregate morphology remains intact in sugar matrix. Upon cooling down from room temperature to 78 K, we find that the full-width at half-maximum (FWHM) of Cy7-DPA peak narrows from 463 cm -1 to 303 cm -1 (34 %) and red shifts by 150 cm -1 as shown in Figures 3d-e.…”

Section: Resultsmentioning

confidence: 95%

Design Principles for 2-Dimensional Molecular Aggregates using Kasha’s Model: Tunable Photophysics in Near and Shortwave Infrared

Deshmukh

Koppel²,

Chuang³

et al. 2019

Preprint

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Technologies which utilize near-infrared (700 – 1000 nm) and short-wave infrared (1000 – 2000 nm) electromagnetic radiation have applications in deep-tissue imaging, telecommunications and satellite telemetry due to low scattering and decreased background signal in this spectral region. It is therefore necessary to develop materials that absorb light efficiently beyond 1000 nm. Transition dipole moment coupling (e.g. J-aggregation) allows for redshifted excitonic states and provides a pathway to highly absorptive electronic states in the infrared. We present aggregates of two cyanine dyes whose absorption peaks redshift dramatically upon aggregation in water from ~800 nm to 1000 nm and 1050 nm respectively with sheet-like morphologies and high molar absorptivities (e ~ 105 M-1cm-1). We use Frenkel exciton theory to extend Kasha’s model for J and H aggregation and describe the excitonic states of 2-dimensional aggregates whose slip is controlled by steric hindrance in the assembled structure. A consequence of the increased dimensionality is the phenomenon of an intermediate “I-aggregate”, one which redshifts yet displays spectral signatures of band-edge dark states akin to an H-aggregate. We distinguish between H-, I- and J-aggregates by showing the relative position of the bright (absorptive) state within the density of states using temperature dependent spectroscopy. I-aggregates hold potential for applications as charge injection moieties for semiconductors and donors for energy transfer in NIR and SWIR. Our results can be used to better design chromophores with predictable and tunable aggregation with new photophysical properties.

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Observation of Vibronic-Coupling-Mediated Energy Transfer in Light-Harvesting Nanotubes Stabilized in a Solid-State Matrix

Cited by 19 publications

References 55 publications

Interplay between structural hierarchy and exciton diffusion in artificial light harvesting

Interplay between structural hierarchy and exciton diffusion in artificial light harvesting

Quantum Biology: An Update and Perspective

Design Principles for 2-Dimensional Molecular Aggregates using Kasha’s Model: Tunable Photophysics in Near and Shortwave Infrared

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