Exciton Coupling Research Articles

Tunable Kerker Scattering in a Self‐Coupled Polaritonic Metasurface

AbstractThe strong coupling between electronic transitions and resonant cavity modes, facilitated by coherent energy transfer, presents unprecedented opportunities for tailoring the photoelectronic properties of constituent components. Here, the concept of Kerker effect is leveraged to demonstrate the dynamic control of scattering directionality in dielectric nanostructures by tuning the exciton‐photon coupling. First, theoretical evidence for a significant modification of the scattering directionality of a dielectric metastructure engineered by excitonic polaritons is provided. As a proof of concept, self‐coupled metasurfaces composed of bulk MoS2, which exhibit a forward/backward scattering ratio up to 20, are constructed. Importantly, tunable directionality is achieved by thermally controlling the excitonic coupling to the Mie modes. The simulated results are in good agreement with the experimental measurements, and the subsequent multipole decompositions effectively elucidate the underlying mechanism, attributed to the interplay between electric and magnetic dipole modes that are modified by excitons. The findings shed light on the control of light flow in the far field through coherent light–matter interactions, thereby opening up numerous possibilities for active optical antennas and quantum emitters on a nanoscale.

J-Aggregation Strategy toward Potentiated NIR-II Fluorescence Bioimaging of Molecular Fluorophores.

Molecular fluorophores emitting in the second near-infrared (NIR-II, 1000-1700 nm) window with strong optical harvesting and high quantum yields hold great potential for in vivo deep-tissue bioimaging and high-resolution biosensing. Recently, J-aggregates are harnessed to engineer long-wavelength NIR-II emitters and show unique superiority in tumor detection, vessel mapping, surgical navigation, and phototheranostics due to their bathochromic-shifted optical bands in the required slip-stacked arrangement aggregation state. However, despite the preliminary progress of NIR-II J-aggregates and theoretical study of structure-property relationships, further paradigms of NIR-II J-aggregates remain scarce due to the lack of study on aggregated fluorophores with slip-stacked fashion. In this effort, how to utilize the specific molecular structure to form slip-stacked packing motifs with J-type aggregated exciton coupling is emphatically elucidated. First, several molecular regulating strategies to achieve NIR-II J-aggregates containing intermolecular interactions and external conditions are positively summarized and deeply analyzed. Then, the recent reports on J-aggregates for NIR-II bioimaging and theranostics are systematically summarized to provide a clear reference and direction for promoting the development of NIR-II organic fluorophores. Eventually, the prospective efforts on ameliorating and promoting NIR-II J-aggregates to further clinical practices are outlined.

Hyperconjugative Aromaticity-Based Circularly Polarized Luminescence Enhancement in Polyaurated Heterocycles.

Hyperconjugative aromaticity (HA) frequently appears in metalla-aromatics, but its effect on photophysical properties remains unexplored to date. Herein, we reveal two different HA scenarios in nearly isostructural triaurated indolium and benzofuranylium compounds. The biased HAs show a discernible effect on the spatial arrangement of metal atoms and thus tailor metal parentage in frontier orbitals and the HOMO-LUMO energy gap. Theoretical calculations and structural analyses demonstrate that HA not only influences the degree of electron delocalization over the trimetalated aromatic rings but also affects π-coordination of Au(I) and intercluster aurophilic interaction. Consequently, the triaurated benzofuranylium complex shows better photoluminescence performance (quantum yield up to 49.7%) over the indolium analogue. Furthermore, four pairs of axially chiral bibenzofuran-centered trinuclear and hexanuclear gold clusters were purposefully synthesized to correlate their HA-involved structures with the chiroptical response. The triaurated benzofuranylium complexes exhibit strong circular dichroism (CD) response in solution but CPL silence even in solid film. In contrast, the hexa-aurated homologues display strong CD and intense CPL signals in both aggregated state and solid film (luminescence anisotropy factor glum up to 10-3). Their amplified chiroptical response is finally ascribed to the dominant intermolecular exciton couplings of large assemblies formed through the HA-tailored aggregation of hexanuclear compounds.

Solid‐State Absorption, Luminescence, and Singlet Fission of Furanyl‐Substituted Diketopyrrolopyrroles with Different π‐Stacking Arrangements

AbstractSmall modifications of the diketopyrrolopyrrole (DPP) molecular structure induced remarkable changes in its spectral and photophysical behavior. Using furan (F) heterosubstitution instead of thiophene (T) substituent resulted in a small blue shift and decreased Huang‐Rhys factor of the absorption spectra in solution, irrespectively to N,N'‐alkyls. Branching of alkyl side chains by formal 2‐ethylation of n‐hexyl substituent (C6 to EH) switched the slipped‐stack arrangement, irrespectively on the heteroatoms. Consequent changes in steady‐state absorption spectra of thin films were interpreted using time dependent density functional theory calculations, carried out on model dimers. Solid‐state luminescence is weak and partially dependent on an excitation wavelength. Singlet fission was observed by femtosecond transient absorption spectroscopy, with considerably different yields for variously π‐stacked FDPP‐EH (30 %) and FDPP‐C6 (160 %). The shape of triplet‐triplet absorption spectra was also influenced by various π‐stacking. The results are discussed in terms of different mixing of both Frenkel and charge transfer states in model dimers and different excitonic and electronic coupling in both types of π‐stacks, visualized by natural transition orbitals.

Fused-Ring Electron-Acceptor Single Crystals with Chiral 2D Supramolecular Organization for Anisotropic Chiral Optoelectronic Devices.

Supramolecular chiral organization gives π-conjugated molecules access to fascinating specific interactions with circularly polarized light (CPL). Such a feature enables the fabrication of high-performance chiral organic electronic devices that detect or emit CPL directly. Herein, it is shown that chiral fused-ring electron-acceptor BTP-4F single-crystal-based phototransistors demonstrate distinguished CPL discrimination capability with current dissymmetry factor exceeding 1.4, one of the highest values among state-of-the-art direct CPL detectors. Theoretical calculations prove that the chirality at the supramolecular level in these enantiomeric single crystals originates from chiral exciton coupling of a unique quasi-2Dsupramolecular organization consisting of interlaced molecules with opposite helical conformation. Impressively, such supramolecular organization produces a higher dissymmetry factor along the preferred growth direction of the chiral single crystals in comparison to that of the short axis direction. Furthermore, the amplified, inverted, and also anisotropic current dissymmetry compared to optical dissymmetry is studied by finite element simulations. Therefore, a unique chiral supramolecular organization that is responsible for the excellent chiroptical response and anisotropic electronic properties is developed, which not only enables the construction of high-performance CPL detection devices but also allows a better understanding of the structure-property relationships in chiral organic optoelectronics.

A quantum trajectory picture of single photon absorption and energy transport in photosystem II.

We use quantum trajectory theory to study the dynamics of the first step in photosynthesis for a single photon interacting with photosystem II (PSII). By considering individual trajectories we are able to look beyond the ensemble average dynamics to compute the PSII system evolution conditioned upon individual photon counting measurements. Measurements of the transmitted photon beam strongly affects the system state, since detection of an outgoing photon confirms that the PSII must be in the electronic ground state, while a null measurement implies it is in an excited electronic state. We show that under ideal conditions, observing the null result transforms a state with a low excited state population to a state with nearly all population contained in the excited states. We study the PSII dynamics conditioned on such photon counting for both a pure excitonic model of PSII and a more realistic model with exciton-phonon coupling to a dissipative phononic environment. In the absence of such coupling, we show that the measured fluorescence rates show oscillations constituting a photon-counting witness of excitonic coherence. Excitonic coupling to the phonon environment has a strong effect on the observed rates of fluorescence, damping the oscillations. Addition of non-radiative decay and incoherent transitions to radical pair states in the reaction center to the phononic model allows extraction of a quantum efficiency of 92.5% from the long-time evolution, consistent with bulk experimental measurements.

Solution-processed halide perovskite microcavity exciton-polariton light-emitting diodes working at room temperature

Exciton-polaritons offer the potential to achieve electrically pumped perovskite polariton lasers with much lower current thresholds than conventional photonic lasers. While optically pumped exciton-polaritons have been widely studied in halide perovskites, electrically-pumped polaritons remain limited. In this study, we demonstrate the use of a solution-processing strategy to develop halide perovskite polariton light-emitting diodes (LEDs) that operate at room temperature. The strong coupling of excitons and cavity photons is confirmed through the dispersion relation from angle-resolved reflectivity, with a Rabi splitting energy of 64 meV. Our devices exhibit angle-resolved electroluminescence following the low polariton branch and achieve external quantum efficiencies of 1.7%, 3.85%, and 3.7% for detunings of 1.1, −77, and −128 meV, respectively. We also explore devices with higher efficiency of 5.37% and a narrower spectral bandwidth of 6.5 nm through the optimization of a top emitting electrode. Our work demonstrates, to our knowledge, the first room-temperature perovskite polariton LED with a typical vertical geometry and represents a significant step towards realizing electrically pumped perovskite polariton lasers.

Structural comparison of allophycocyanin variants reveals the molecular basis for their spectral differences.

Allophycocyanins are phycobiliproteins that absorb red light and transfer the energy to the reaction centers of oxygenic photosynthesis in cyanobacteria and red algae. Recently, it was shown that some allophycocyanins absorb far-red light and that one subset of these allophycocyanins, comprising subunits from the ApcD4 and ApcB3 subfamilies (FRL-AP), form helical nanotubes. The lowest energy absorbance maximum of the oligomeric ApcD4-ApcB3 complexes occurs at 709nm, which is unlike allophycocyanin (AP; ApcA-ApcB) and allophycocyanin B (AP-B; ApcD-ApcB) trimers that absorb maximally at ~ 650nm and ~ 670nm, respectively. The molecular bases of the different spectra of AP variants are presently unclear. To address this, we structurally compared FRL-AP with AP and AP-B, performed spectroscopic analyses on FRL-AP, and leveraged computational approaches. We show that among AP variants, the α-subunit constrains pyrrole ring A of its phycocyanobilin chromophore to different extents, and the coplanarity of ring Awith rings B and C sets a baseline for the absorbance maximum of the chromophore. Upon oligomerization, the α-chromophores of all AP variants exhibit a red shift of the absorbance maximum of ~ 25 to 30nm and band narrowing. We exclude excitonic coupling in FRL-AP as the basis for this red shift and extend the results to discuss AP and AP-B. Instead, we attribute these spectral changes to a conformational alteration of pyrrole ring D, which becomes more coplanar with rings B and C upon oligomerization. This study expands the molecular understanding of light-harvesting attributes of phycobiliproteins and will aid in designing phycobiliproteins for biotechnological applications.

One‐Photon and Two‐Photon Absorption Properties of Multi‐Branched Squaraine Dyes Comprised of Triphenylamine Cores and Ethynylene Linkers

AbstractWe developed multi‐branched π‐conjugated systems using squaraine dyes with triphenylamine cores connected by ethynylene linkers. We investigated the influence of interbranch coupling between squaraine branches on their one‐photon (OPA) and two‐photon absorption (TPA) properties. These dyes with triphenylamine components showed a red‐shifted one‐photon absorption (OPA) compared to the precursor squaraine dyes. Among branched dyes, the lack of apparent splitting or shift in the absorption maxima, even as the absorption intensity increased with the number of chromophores, implies the presence of limited exciton coupling between the squaraine branches. The present squaraine dyes with triphenylamine cores exhibited a moderate TPA compared to the precursor squaraine without the triphenylamine core, due to the extended π‐conjugation. Notably, both the 3‐branched and 2‐branched dyes demonstrated additional enhancement in the TPA response, surpassing that of the monochromophoric counterpart. This resulted in achieving a substantial TPA cross section of up to 3905 GM at 830 nm.

Symmetry-Breaking Charge Separation in a Chiral Bis(perylenediimide) Probed at Ensemble and Single-Molecule Levels.

Chiral molecular assemblies exhibiting symmetry-breaking charge separation (SB-CS) are potential candidates for the development of chiral organic semiconductors. Herein, we explore the excited-state dynamics of a helically chiral perylenediimide bichromophore (Cy-PDI2) exhibiting SB-CS at the ensemble and single-molecule levels. Solvent polarity-tunable interchromophoric excitonic coupling in chiral Cy-PDI2 facilitates the interplay of SB-CS and excimer formation in the ensemble domain. Analogous to the excited-state dynamics of Cy-PDI2 at the ensemble level, single-molecule fluorescence lifetime traces of Cy-PDI2 depicted long-lived off-states characteristic of the radical ion pair-mediated dark states. The discrete electron transfer and charge separation dynamics in Cy-PDI2 at the single-molecule level are governed by the distinct influence of the local environment. The present study aims at understanding the fundamental excited-state dynamics in chiral organic bichromophores for designing efficient chiral organic semiconductors and applications toward charge transport materials.

Resonant optical reflection from a GaN/(Al,Ga)N excitonic Bragg structure

We experimentally demonstrate the formation of a superradiant optical mode in the room-temperature reflection spectra from a resonant Bragg structure composed of 30 equidistant GaN quantum wells separated by (Al,Ga)N barriers. The mode arises when the condition of the Bragg diffraction is fulfilled at the wavelength corresponding to the energy of the quasi-two-dimensional excitons in the quantum wells. It manifests itself as a significant increase in the amplitude and a change in the shape of the resonant optical reflection due to the electromagnetic coupling of the excitons. By modeling of the optical spectra, we evaluate the radiative and non-radiative broadening parameters of the excitonic states in the GaN quantum wells, which appear to be 0.4 ± 0.02 and 40 ± 5 meV, correspondingly, for the resonant exciton energy of 3.605 eV. The resonant Bragg structure based on the periodic sequence of the GaN quantum wells demonstrates an efficient coupling of photons and excitons at room temperature, which makes it promising for device applications.

Enhanced Chiral Exciton Coupling in Neat Molecular Films

Enhanced Chiral Exciton Coupling in Neat Molecular Films

Electronic Structure, Spectroscopy, and Redox Properties of Highly Soluble (μ-oxo)Bis[Tetra(tert-butyl)(phthalocyaninato)Iron(III)] Complex and Its Pyridine Adduct Under Anaerobic Conditions in Non-Coordinating Solvents

The solid-state Mössbauer spectra of a highly soluble (μ-oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] complex 1 ((PctBuFe)2O) consist of two doublets that represent bent geometry μ-oxo(1) (1a, ΔEQ = 0.43 mm/s, T = 10K) and linear geometry μ-oxo(2) (1b) isomers (ΔEQ = 1.40 mm/s, T = 10K) with the ratio between two isomers depending on the purification method. Both isomers were found to be diamagnetic and transform entirely in 1a isomer in solution. The room- and low-temperature MCD spectra of 1a show one Faraday A- and one B-terms between 670 and 720 nm, which correlate with the 690 nm band and 709 nm shoulder observed in the UV-Vis spectrum of this compound. UV-Vis and MCD spectra of 1a are independent of the temperature. Both 1a and 1b are diamagnetic between room temperature and 4 K. Electrochemical experiments show up to three oxidation and up to four reduction processes in 1a. Its oxidation under spectroelectrochemical or chemical (in the absence of oxygen-containing oxidants) oxidation conditions in non-coordinating solvents results in the formation of a broad NIR band around 1195 nm (first oxidation) and 1264 nm (second oxidation). The MCD spectra of the redox-active species show a Faraday B-term signal with negative amplitude in this region and are very different from those in monomeric PctBu(1-)FeIIIX2 complexes 5X (X = Cl- or CF3CO2 -). Pyridine adduct of 1a ((PyPctBuFe)2O; 2Py) is paramagnetic (μB = 2.19, g = 2.11, and J = -6.1cm-1) and has a major peak at 627 nm in UV-Vis spectrum, which is associated with MCD pseudo A-term. Density Functional Theory (DFT) and Time-Dependent DFT (TDDFT) calculations, along with Kasha’s and Spano’s exciton coupling theories, were used to explain unusually red-shifted intense transitions in 1a as well as H-aggregate like spectra of the pyridine adduct 2Py.

Radiative suppression of exciton–exciton annihilation in a two-dimensional semiconductor

Two-dimensional (2D) semiconductors possess strongly bound excitons, opening novel opportunities for engineering light–matter interaction at the nanoscale. However, their in-plane confinement leads to large non-radiative exciton–exciton annihilation (EEA) processes, setting a fundamental limit for their photonic applications. In this work, we demonstrate suppression of EEA via enhancement of light–matter interaction in hybrid 2D semiconductor–dielectric nanophotonic platforms, by coupling excitons in WS2 monolayers with optical Mie resonances in dielectric nanoantennas. The hybrid system reaches an intermediate light–matter coupling regime, with photoluminescence enhancement factors up to 102. Probing the exciton ultrafast dynamics reveal suppressed EEA for coupled excitons, even under high exciton densities >1012 cm−2. We extract EEA coefficients in the order of 10−3, compared to 10−2 for uncoupled monolayers, as well as a Purcell factor of 4.5. Our results highlight engineering the photonic environment as a route to achieve higher quantum efficiencies, for low-power hybrid devices, and larger exciton densities, towards strongly correlated excitonic phases in 2D semiconductors.

Minimizing non-radiative decay in molecular aggregates through control of excitonic coupling

The widely known “Energy Gap Law” (EGL) predicts a monotonically exponential increase in the non-radiative decay rate (knr) as the energy gap narrows, which hinders the development of near-infrared (NIR) emissive molecular materials. Recently, several experiments proposed that the exciton delocalization in molecular aggregates could counteract EGL to facilitate NIR emission. In this work, the nearly exact time-dependent density matrix renormalization group (TD-DMRG) method is developed to evaluate the non-radiative decay rate for exciton-phonon coupled molecular aggregates. Systematical numerical simulations show, by increasing the excitonic coupling, knr will first decrease, then reach a minimum, and finally start to increase to follow EGL, which is an overall result of two opposite effects of a smaller energy gap and a smaller effective electron-phonon coupling. This anomalous non-monotonic behavior is found robust in a number of models, including dimer, one-dimensional chain, and two-dimensional square lattice. The optimal excitonic coupling strength that gives the minimum knr is about half of the monomer reorganization energy and is also influenced by system size, dimensionality, and temperature.

Excitonic Coupling in Fluorene-Based Bichromophoric Systems: Vibrational Quenching and the Transition from Weak to Intermediate Coupling.

Excimeric systems (i.e., excited dimers) have well served as model compounds for the study of the delocalization of electronic energy over weakly interacting chromophores. However, there remain relatively few isolated systems in which such interactions can be studied experimentally at a level to afford detailed comparisons with theory. In this Article, we examine a series of covalently and noncovalently linked dimers of fluorene, as a model aromatic chromophore, where the formation of excimers requires a π-stacked, cofacial orientation at van der Waals contact. Building upon a series of seminal prior studies that examined vibronic quenching of the excitation interaction in van der Waals dimers, the key question that we sought to address here is whether a single quenching factor could reproduce experimental excitonic splittings across a series of covalently and noncovalently linked bichromophoric systems built from the same chromophore. In comparing experimentally measured excitonic splittings with calculated static splittings using time-dependent density functional methods, we find that all systems save one fall on a line with a slope of 0.080(8), reflecting a vibrational quenching of roughly 1 order of magnitude. The outlier, which shows a significantly reduced quenching factor, represents a cyclophane-linked system where the fluorene moieties are constrained in a cofacial arrangement. We argue that this system evidences the transition from the weak to intermediate coupling regime.

A general design of pyridinium-based fluorescent probes for enhancing two-photon microscopy

Two-photon absorbing fluorescent probes have emerged as powerful imaging tools for subcellular-level monitoring of biological substances and processes, offering advantages such as deep light penetration, minimal photodamage, low autofluorescence, and high spatial resolution. However, existing two-photon absorbing probes still face several limitations, such as small two-photon absorption cross-section, poor water solubility, low membrane permeability, and potentially high toxicity. Herein, we report three small-molecule probes, namely MSP-1arm, Lyso-2arm, and Mito-3arm, composed of a pyridinium center (electron-acceptor) and various methoxystyrene “arms” (electron-donor). These probes exhibit excellent fluorescence quantum yield and decent aqueous solubility. Leveraging the inherent intramolecular charge transfer and excitonic coupling effect, these complexes demonstrate excellent two-photon absorption in the near-infrared region. Notably, Lyso-2arm and Mito-3arm exhibit distinct targeting abilities for lysosomes and mitochondria, respectively. In two-photon microscopy experiments, Mito-3arm outperforms a commercial two-photon absorbing dye in 2D monolayer HeLa cells, delivering enhanced resolution, broader NIR light excitation window, and higher signal-to-noise ratio. Moreover, the two-photon bioimaging of 3D human forebrain organoids confirms the successful deep tissue imaging capabilities of both Lyso-2arm and Mito-3arm. Overall, this work presents a rational design strategy in developing competent two-photon-absorbing probes by varying the number of conjugated “arms” for bioimaging applications.

Theoretical Insights into Aggregation-Induced Emission with the Ionic π Fluorophore: The Importance of Choosing the Dimer QM Model in the ONIOM Study.

In understanding the mechanism of aggregation-induced emission (AIE), the multilevel ONIOM framework has been demonstrated as one of the efficient tools that can capture the essential mechanistic information by choosing a single fluorophore as the quantum mechanics (QM) model and putting all surrounding molecules in the low-level region. Recently, the ionic styryl-pyridine salt (namely, SPH) has been reported as a new class of AIEgen with a high fluorescence yield. In the SPH crystal, a pair of ionic SPH molecules are closely stacked with each other in an antiparallel, head-to-tail pattern, thus the choice of QM models (an individual or dimeric structure) becomes critical in the ONIOM study. Herein we report the AIE mechanism of the ionic SPH at the QM ((TD)-CAM-B3LYP) and ONIOM(QM:MM) levels. As usual, the fluorescence quenching of SPH in tetrahydrofuran (THF) solution is attributed to a nonradiative relaxation via the central C═C bond rotation, with a rather low barrier of 2.7 kcal/mol. In crystals, either with a monomer or dimer model, the fluorescence quenching channel is found to be restricted due to the obvious C═C rotation barriers. Compared with the monomer model, the dimer model, by treating the orbital interaction of the two SPH molecules at the QM level, provides significantly increased barriers and a red-shifted emission wavelength that better matches the experimental value. In addition, the calculated exciton coupling in the fluorescence emission state can be discovered only by a dimer model. The findings here emphasize not only the importance of choosing a proper model in the ONIOM study of AIE but also expanding our understanding of novel AIE systems.

Magneto-optics in a van der Waals magnet tuned by self-hybridized polaritons.

Controlling quantum materials with light is of fundamental and technological importance. By utilizing the strong coupling of light and matter in optical cavities1-3, recent studies were able to modify some of their most defining features4-6. Here we study the magneto-optical properties of a van der Waals magnet that supports strong coupling of photons and excitons even in the absence of external cavity mirrors. In this material-the layered magnetic semiconductor CrSBr-emergent light-matter hybrids called polaritons are shown to substantially increase the spectral bandwidth of correlations between the magnetic, electronic and optical properties, enabling largely tunable optical responses to applied magnetic fields and magnons. Our results highlight the importance of exciton-photon self-hybridization in van der Waals magnets and motivate novel directions for the manipulation of quantum material properties by strong light-matter coupling.

Tunable Non-Kasha Behaviors and Excited-State Dynamics of Quadrupolar Squaraine Aggregates.

Versatile coupling theories have been developed for rationalizing unusual aggregation phenomena of multipolar chromophores. Here, diverse excitonic couplings of a quadrupolar squaraine dye protonated by trifluoroacetic acid could be achieved and tuned unprecedentedly in different solvation media. Subtle changes of the solvent and ion pair influenced the aggregation of the donor-acceptor-donor (D-A-D)-type SQC6 and led to significant variations in optical properties. In contrast to conventional H/J aggregates, strong spectroscopic evidence of nonfluorescent and red-shifted hJ aggregation was obtained. Assumptions of the excitonic interplay with variable strength stabilized by the synergic contributions of π-π stacking and electronic interaction were addressed. Comparative excited-state dynamics in the aggregates clarified the distinctive excitonic coupling of adjacent quadrupolar molecules and the nature of the excited state beyond the dimers. Meanwhile, dominant two-photon absorption transitions could be elucidated by a resonance-enhanced mechanism. The present unusual molecular interplay provides a strategy to fine tune the optical properties of multipolar aggregates.