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

Pruchyathamkorn, Jiratheep; Kendrick, William J.; Frawley, Andrew T.; Mattioni, Andrea; Caycedo‐Soler, Felipe; Huelga, Susana F.; Plenio, Martin B.; Anderson, Harry L.

doi:10.1002/ange.202006644

Cited by 11 publications

(3 citation statements)

References 38 publications

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“…An intriguing question is whether this is an accidental coincidence or whether the broad minimum emerging in the decay rate, which is thus robust against small fluctuations in the emitters position, can play a relevant role in the energy transfer and the light harvesting processes. As already anticipated, the study of the optical properties of two (or more) coupled nanorings is motivated by the existence of similar structures in nature that enable efficient light harvesting and energy transfer [35,[54][55][56][57][58][59][60][61][62][63][64]. Indeed, while most biological systems are soft and disordered, photosynthetic complexes in certain purple bacteria exhibit crystalline order.…”

Section: B Two Coupled Nanoringsmentioning

confidence: 99%

Optical Properties of Concentric Nanorings of Quantum Emitters

Scheil¹,

Holzinger²,

Moreno-Cardoner³

et al. 2023

Preprint

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A ring of sub-wavelength spaced dipole-coupled quantum emitters features extraordinary optical properties when compared to a one-dimensional chain or a random collection of emitters. One finds the emergence of extremely subradiant collective eigenmodes similar to an optical resonator, which feature strong 3D sub-wavelength field confinement. Motivated by structures commonly appearing in natural light harvesting complexes, we extend these studies to stacked concentric multi-ring geometries. We predict that double rings allow to engineer significantly darker and better confined collective excitation states over a broader energy band compared to the single ring case. These potentially enhance weak field absorption and low loss excitation energy transport. For the specific geometry of the three rings appearing in the natural LH2 antenna we show that the coupling between the lower double ring structure and the higher energy blue shifted single ring is very close to a critical value for the actual size of the molecule. This creates collective excitations with significant contributions from all three rings as a vital ingredient for efficient and fast coherent inter-ring transport. Such a geometry thus should prove useful for the design of sub-wavelength weak field antennas.

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Section: B Two Coupled Nanoringsmentioning

confidence: 99%

Optical Properties of Concentric Nanorings of Quantum Emitters

Scheil¹,

Holzinger²,

Moreno-Cardoner³

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…However, their fluorescence quantum yield (QY) is limited by aggregation‐caused quenching (ACQ) upon incorporation into LHA. [ 38,39 ] To overcome this limitation, chemists have developed dendrimers, [ 40,41 ] artificial light‐harvesting complexes, especially those based on large macrocycles, [ 42–44 ] assemblies based on aggregation‐induced emission (AIE) [ 14,45–48 ] and other organic dyes, [ 47,49,50 ] and conjugated polymers. [ 51–53 ] In these organic systems, rational molecular design can minimize ACQ, which ensures their high fluorescence brightness and efficient energy transfer.…”

Section: Introductionmentioning

confidence: 99%

Giant Light‐Harvesting in Dye‐Loaded Nanoparticles Enhanced by Blank Hydrophobic Salts

Biswas,

Melnychuk,

Severi

et al. 2023

Advanced Optical Materials

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Light‐harvesting is a fundamental process in nature, which inspires researchers to develop artificial systems for photocatalysis, photovoltaics, and biosensing. A previously introduced light‐harvesting nanoantenna, based on polymeric nanoparticles (NPs) loaded with rhodamine dyes and bulky hydrophobic counterions, provides a record‐breaking antenna effect ≈1000. However, the high dye cooperativity of its thousands of encapsulated dyes causes energy losses by traces of self‐quenched dye aggregates. Here, it is found that these imperfections can be suppressed by blank hydrophobic salts (BHS) formed by the same bulky counterion (fluorinated tetraphenylborate) with an optically inactive cation, analogs of ionic liquids. The presence of BHS increases twofold the fluorescence quantum yields and fluorescence lifetimes of NPs and suppresses their fluorescence blinking. This study assumes that BHS provides an excess of bulky counterions that excludes traces of dye aggregates. As a result, an efficient Forster resonance energy transfer (FRET) is achieved from 40 000 dye donors to a single acceptor within a 70 nm particle, leading to the antenna effect of 4800, which is by far the highest value reported to date. Using this nanoantenna, a single‐molecule detection of the FRET acceptor is realized at low excitation power using an RGB camera of a smartphone.

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“…systems featuring circularly polarized luminescence (CPL) by intraassembly chirality transfer 18 , charge-transfer in donor-acceptor systems 19 , and cooperative catalysis [20][21][22] . In only few of the most complicated self-assembled systems reported to date, more than two differentiable functionalities, situated on separate components, have been involved 20,23,24 .…”

mentioning

confidence: 99%

Evolution of Multicomponent [Pd2ABCD] Cages

Benchimol

Baksi

et al. 2023

Preprint

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Synthetic supramolecules, inspired by biological hosts, catalysts and machines, promise to find application in sustainable synthesis, separation, energy conversion and medicine. However, the implementation of multiple functionalities within distinct self- assembled structures still poses considerable challenges. In particular metal-mediated assemblies are difficult to form from multiple chemically different building blocks without falling into narcissistic self-sorting or a statistical mess. Here we report a systematic series of integratively self-assembled heteroleptic cages in which two square-planar PdII cations are bridged by four chemically different bis-pyridyl ligands A, B, C and D via a collection of synergistic effects to form a single isomer of lantern-shaped cage [Pd2ABCD] as exclusive product. This ultimate self-sorting goal, forming just one out of 55 possible structures, is reached under full thermodynamic control and can be realized progressively (by combining heteroleptic progenitors such as [Pd2A2C2] with [Pd2B2D2]), directly from ligands and PdII cations, or most impressively by mixing all four corresponding homoleptic cages. Structural and mechanistic details were comprehensively examined by NMR and mass spectrometry and nine single crystal X-ray structures. The rational design of complex multicomponent assemblies, formed in high yield under thermodynamic control, allows to incorporate different chemical moieties in a modular approach and advance the application level of functional nanosystems.

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

Cited by 11 publications

References 38 publications

Optical Properties of Concentric Nanorings of Quantum Emitters

Optical Properties of Concentric Nanorings of Quantum Emitters

Giant Light‐Harvesting in Dye‐Loaded Nanoparticles Enhanced by Blank Hydrophobic Salts

Evolution of Multicomponent [Pd2ABCD] Cages

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