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A comprehensive investigation of two new molecular triads incorporating the diketopyrrolopyrrole unit into a quinoidized thienothiophene skeleton, which is further end-capped with dicyanomethylene (DPP-TT-CN) or phenoxyl groups (DPP-TT-PhO), has been carried out. A combination of UV-Vis-NIR and infrared spectroelectrochemical techniques and cryogenic UV-Vis-NIR absorption spectroscopy supported by theoretical calculations has been used. The main result is the formation of similar H-aggregates in the dimerization process of the neutral molecules and of the charged anionic species. The experimental absorption spectra of the aggregated species are accurately reproduced by quantum chemical calculations using the Spano's model, including excitonic coupling for the dimeric forms and full vibronic resolution of the absorption bands. The strong excitonic coupling taking place is key to understand the electronic structure of the dimeric aggregates and has been instrumental to disentangle the type of H-aggregation. This study is of relevance to get a better understanding of the molecular aggregation of organic p-conjugated chromophores and is useful as a guideline for the refinement of the engineering of molecular materials for which supramolecular design is required.

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The exciton interaction of four chlorophyll a (Chl a) molecules in a symmetrical tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP was analyzed in the pH range of 3-11. Exciton splitting ΔE = 232 ± 2 cm-1 of the Qy band of Chl a into two subcomponents with relative intensities of 78.1 ± 0.7 % and 21.9 ± 0.7 % was determined by a joint decomposition of the absorption and circular dichroism spectra into Gaussian functions. The exciton coupling parameters were calculated based on the BoWSCP atomic structure in three approximations: the point dipole model, the distributed atomic monopoles, and direct ab initio calculations in the TDDFT/PCM approximation. The Coulomb interactions of monomers were calculated within the continuum model using three values of optical permittivity. The models based on the properties of free Chl a in solution suffer from significant errors both in estimating the absolute value of the exciton interaction and in the relative intensity of exciton transitions. Calculations within the TDDFT/PCM approximation reproduce the experimentally determined parameters of the exciton splitting and the relative intensities of the exciton bands. The following factors of pigment-protein and pigment-pigment interactions were examined: deviation of the macrocycle geometry from the planar conformation of free Chl; the formation of hydrogen bonds between the macrocycle and water molecules; the overlap of wave functions of monomers at close distances. The most significant factor is the geometrical deformation of the porphyrin macrocycle, which leads to an increase in the dipole moment of Chl monomer from 5.5 to 6.9 D and to a rotation of the dipole moment by 15° towards the cyclopentane ring. The contributions of resonant charge-transfer states to the wave functions of the Chl dimer were determined and the transition dipole moments of the symmetric and antisymmetric charge-transfer states were estimated.

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The structural characterization of nonstoichiometric nanographene (NG)-organic hybrid materials is usually difficult. The number of substituents on the edge and their arrangements are frequently questioned but are difficult to answer. Since the number of functional groups is closely related to the distance between the nearest neighbors (dISD ), the extraction of dISD from spectroscopic data could provide important information on their structural characterization. We show that exciton coupling, which is a theoretical prediction of the absolute structures of discrete molecules, is a possible candidate to address this issue. The comparison of the calculated CD spectra of the chiral chromophores extracted from the model NG edge with the observed edge spectra indicated a dISD of ca. 8 Å; this corresponded to substitution on every other armchair edge. Furthermore, an up-up-down-down alternate orientation was found to be a possible edge structure. Although the procedure was limited to NGs carrying chiral substituents, our method could facilitate the detailed structural characterization of NG-organic hybrid materials.

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Neuromorphic visual sensors (NVS) based on photonic synapses hold a significant promise to emulate the human visual system. However, current photonic synapses rely on exquisite engineering of the complex heterogeneous interface to realize learning and memory functions, resulting in high fabrication cost, reduced reliability, high energy consumption and uncompact architecture, severely limiting the up-scaled manufacture, and on-chip integration. Here a photo-memory fundamental based on ion-exciton coupling is innovated to simplify synaptic structure and minimize energy consumption. Due to the intrinsic organic/inorganic interface within the crystal, the photodetector based on monolithic 2D perovskite exhibits a persistent photocurrent lasting about 90 s, enabling versatile synaptic functions. The electrical power consumption per synaptic event is estimated to be≈1.45 × 10-16 J, one order of magnitude lower than that in a natural biological system. Proof-of-concept image preprocessing using the neuromorphic vision sensors enabled by photonic synapse demonstrates 4 times enhancement of classification accuracy. Furthermore, getting rid of the artificial neural network, an expectation-based thresholding model is put forward to mimic the human visual system for facial recognition. This conceptual device unveils a new mechanism to simplify synaptic structure, promising the transformation of the NVS and fostering the emergence of next generation neural networks.

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Constructing chiral plexcitonic systems with tunable plasmon-exciton coupling may advance the scientific exploitation of strong light-matter interactions. Because of their intriguing chiroptical properties, chiral plasmonic materials have shown promising applications in photonics, sensing, and biomedicine. However, the strong coupling of chiral plasmonic nanoparticles with excitons remains largely unexplored. Here we demonstrate the construction of a chiral plasmon-exciton system using chiral AuAg nanorods and J aggregates for tuning the plexcitonic optical chirality. Circular dichroism spectroscopy was employed to characterize chiral plasmon-exciton coupling, in which Rabi splitting and anticrossing behaviors were observed, whereas the extinction spectra exhibited less prominent phenomena. By controlling the number of molecular excitons and the energy detuning between plasmons and excitons, we have been able to fine-tune the plexcitonic optical chirality. The ability to fine-tune the plexcitonic optical chirality opens up unique opportunities for exploring chiral light-matter interactions and boosting the development of emerging chiroptical devices.

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In nanophotonics and quantum optics, we aim to control and manipulate light with tailored nanoscale structures. Hybrid systems of nanostructures and atomically thin materials are of interest here, as they offer rich physics and versatility due to the interaction between photons, plasmons, phonons, and excitons. In this study, we explore the optical and electronic properties of a hybrid system, a naturally n-doped monolayer WS2 covering a gold disk. We demonstrate that the nonresonant excitation of the gold disk in the high absorption regime efficiently generates hot carriers via localized surface plasmon excitation, which n-dope the monolayer WS2 and enhance the photoluminescence emission by regulating the multiexciton population and stabilizing the neutral exciton emission. The results are relevant to the further development of nanotransistors in photonic circuits and optoelectronic applications.

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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 709 nm, which is unlike allophycocyanin (AP; ApcA-ApcB) and allophycocyanin B (AP-B; ApcD-ApcB) trimers that absorb maximally at ~ 650 nm and ~ 670 nm, 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 A with 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 30 nm 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.

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Bacterial outer-membrane multi-heme cytochromes (OMCs) mediate extracellular electron transport (EET). While heme alignment dictates the rate of EET, control of inter-heme coupling in a single OMC remains challenging, especially in intact cells. Given that OMCs diffuse and collide without aggregation on the cell surface, the overexpression of OMCs could increase such mechanical stress to impact the OMCs' protein structure. Here, the heme coupling is modified via mechanical interactions among OMCs by controlling their concentrations. Employment of whole-cell circular dichroism (CD) spectra of genetically engineered Escherichia coli reveals that the OMC concentration significantly impacts the molar CD and redox property of OMCs, resulting in a 4-fold change of microbial current production. The overexpression of OMCs increased the conductive current across the biofilm on an interdigitated electrode, indicating that a higher concentration of OMCs causes more lateral inter-protein electron hopping via collision on the cell surface. The present study would open a novel strategy to increase microbial current production by mechanically enhancing the inter-heme coupling.

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We unambiguously extract the individual decay channels of a coupled plasmon-exciton system by using correlated single-particle absorption and scattering measurements. A remarkable difference in the two channels is present─clear Rabi splitting in the plasmon channel but no Rabi splitting in the exciton channel. Discordance in the absorption and scattering spectra are mainly originated from the distinct contributions of plasmon and exciton channels in the absorption and scattering process. Our findings provide insights into plasmon-exciton interaction in an open cavity and can impact the design of plexcitonic devices for ultrafast nonlinear nanophotonics.

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We show that chiral Frenkel excitons yield intense circularly polarized luminescence with an intrinsic dissymmetry factor in emission glum as high as 0.08. This outstanding value is measured through thin films of cyanine J-aggregates that form twisted bundles. Our measurements, obtained by a Mueller polarization analysis, are artifact-free and reveal a quasi-perfect correlation between the dissymmetry factors in absorption, gabs , and in emission glum . We interpret the bisignate dissymmetry factors as the signature of a strong coupling between chiral Frenkel excitons longitudinally excited along the bundles. We further resolve by polarimetry analysis the split in energy between the excited states with a Davydov splitting as small as 28 meV. We finally show the anti-Kasha nature of the chiral emission bands with opposite optical chirality. These mirror-imaged emissive chiroptical features emerge from the structural rigidity of the bundles that preserves the ground- and excited-state chirality.

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Strong plasmon-exciton coupling, which has potential applications in nanophotonics, plasmonics, and quantum electrodynamics, has been successfully demonstrated by using metallic nanocavities and two-dimensional materials. Dynamical control of plasmon-exciton coupling strength, especially by using optical methods, remains a big challenge although it is highly desirable. Here, we report the optical introduction and manipulation of plasmon-exciton-trion coupling realized in a dielectric-metal hybrid nanocavity, which is composed of a silicon (Si) nanoparticle and a thin gold (Au) film, with an embedded tungsten disulfide (WS2) monolayer. We employ scattering and photoluminescence spectra to characterize the coupling strength between plasmons and excitons in Si/WS2/Au nanocavities constructed by using Si nanoparticles with different diameters. We enhance the plasmon-exciton and plasmon-trion coupling strength by injecting excitons and trions into the WS2 monolayer with a 488 nm laser beam. It is revealed that the emission intensities of excitons and trions with respect to the reference WS2 monolayer can be modified through the change in the coupling strength induced by the laser light. Interestingly, the coupling strength between the plasmons and the excitons/trions can be manipulated from weak to strong coupling regime by simply increasing the laser power, which is clearly resolved in the scattering spectra of Si/WS2/Au nanocavities. More importantly, the plasmon-exciton-trion coupling induced by the laser light is confirmed by the energy exchange between excitons and trions. Our findings indicate the possibility for optically manipulating plasmon-exciton interaction and suggest the practical applications of dielectric-metal hybrid nanocavities in nanoscale plasmonic devices.

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Spatial electronic communications of chromophores are both theoretically and practically fascinating. Despite intramolecular or intermolecular exciton coupling was observed in multichromophoric oligomers and J-aggregates, respectively, it is unusual that they both occur in the same molecule. Herein, ethene-bridged aza-BODIPY dimers with intramolecular exciton splitting have been developed. By encapsulating the dimer into F-127 polymer, J-type aggregated nanoparticles were produced, which showed obvious intermolecular exciton coupling and dramatically redshifted absorption and emission peaks at 936 and 1003 nm, respectively. The fabricated nanoagents have high photothermal conversion ability (η=60.3 %) and are ultra-photostable, leading to complete tumor ablation with 915 nm laser irradiation. This phototherapeutic nanoplatform through modulating both intra- and intermolecular exciton couplings is a valuable paradigm for developing photothermal agents for tumor treatment.

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We report a general synthetic route toward helical ladder polymers with varying spring constants, built with chirality-assisted synthesis (CAS). Under tension and compression, these shape-persistent structures do not unfold, but rather stretch and compress akin classical Hookean springs. Our synthesis is adaptable to helices with different pitch and diameter, which allowed us to investigate how molecular flexibility in solution depends on the exact geometry of the ladder polymers. Specifically, we showed with molecular dynamic simulations and by measuring the longitudinal 1 H NMR relaxation times (T1 ) for our polymers at different Larmor frequencies, that increasing the helix diameter leads to increased flexibility. Our results present initial design rules for tuning the mechanical properties of intrinsically helical ladder polymers in solution, which will help inspire a new class of robust, spring-like molecular materials with varying mechanical properties.

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Fluorescent conjugation can be considered as the chromophoric derivatization of the target, and as such, it may provide additional structure-related information available by using circular dichroism (CD) spectroscopy. In this essay, peculiar CD spectroscopic data reported earlier for thyroid hormone-rhodamine conjugates have been re-evaluated. Contrary to the original proposal on the intramolecular folding of the labelled hormone, the bisignate motif observed in the CD spectrum is a clear evidence of dye-dye intermolecular chiral exciton coupling, indicating supramolecular self-association of the conjugates. This anomalous solution behaviour undermines the credibility of experimental results reported with such conjugates still being used in the laboratory practice. The extension of routine far-ultraviolet (UV) CD spectroscopic scans of chiral fluorophore conjugates into the near-UV and visible spectral region is strongly recommended.

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We studied the kinetics of the reaction of N-acetyl-l-cysteine (NAC or RSH) with cupric ions at an equimolar ratio of the reactants in aqueous acid solution (pH 1.4−2) using UV/Vis absorption and circular dichroism (CD) spectroscopies. Cu2+ showed a strong catalytic effect on the 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radical (ABTSr) consumption and autoxidation of NAC. Difference spectra revealed the formation of intermediates with absorption maxima at 233 and 302 nm (ε302/Cu > 8 × 103 M−1 cm−1) and two positive Cotton effects centered at 284 and 302 nm. These intermediates accumulate during the first, O2-independent, phase of the NAC autoxidation. The autocatalytic production of another chiral intermediate, characterized by two positive Cotton effects at 280 and 333 nm and an intense negative one at 305 nm, was observed in the second reaction phase. The intermediates are rapidly oxidized by added ABTSr; otherwise, they are stable for hours in the reaction solution, undergoing a slow pH- and O2-dependent photosensitive decay. The kinetic and spectral data are consistent with proposed structures of the intermediates as disulfide-bridged dicopper(I) complexes of types cis-/trans-CuI2(RS)2(RSSR) and CuI2(RSSR)2. The electronic transitions observed in the UV/Vis and CD spectra are tentatively attributed to Cu(I) → disulfide charge transfer with an interaction of the transition dipole moments (exciton coupling). The catalytic activity of the intermediates as potential O2 activators via Cu(II) peroxo-complexes is discussed. A mechanism for autocatalytic oxidation of Cu(I)−thiolates promoted by a growing electronically coupled −[CuI2(RSSR)]n− polymer is suggested. The obtained results are in line with other reported observations regarding copper-catalyzed autoxidation of thiols and provide new insight into these complicated, not yet fully understood systems. The proposed hypotheses point to the importance of the Cu(I)−disulfide interaction, which may have a profound impact on biological systems.

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Cysteine (Cys) can serve as a biomarker to indicate diseases or disorders, and its chiral sensing has attracted increasing attention. Herein, we established an ultrasound-facilitated chiral sensing method for Cys using 4-chloro-7-nitro-1,2,3-benzoxadiazole (NBD-Cl) and electronic circular dichroism (ECD) spectroscopy. The formation of chiral disulfide bonds induced degenerate exciton coupling between two NBD chromophores, resulting in intense Cotton effects (CEs) of the sensing product. The anisotropy factor (g) was linearly correlated with the enantiomeric excess of Cys across the visible region (400-500 nm), and other natural amino acids or biothiols did not interfere with the detection. This ultrasound-promoted efficient and specific chiral sensing method of Cys has potential for application in the diagnosis of related diseases.

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Fluorescent labeling is a broadly utilized approach to assess in vitro and in vivo behavior of biologically active, especially cell-penetrating and antimicrobial peptides. In this communication, far-UV circular dichroism (CD) spectra of penetratin (PEN) fluorophore conjugates reported previously have been re-evaluated. Compared to the intrinsically disordered native peptide, rhodamine B and carboxyfluorescein derivatives of free and membrane-bound PEN exhibit extrinsic CD features. Potential sources of these signals displayed above 220 nm are discussed suggesting the contributions of both intra- and intermolecular chiral exciton coupling mechanisms. Careful evaluation of the CD spectra of fluorophore-labeled peptides is a valuable tool for early detection of labeling-provoked structural alterations which in turn may modify the membrane binding and cellular uptake compared to the unconjugated form.

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Nanomaterials with a defined composition and structure can be synthesized by exploiting natural templates or biomolecular matrices. In the present work, we use protein nanocages derived from human ferritin as a nanoscale building block for the assembly of gold nanoparticles and fluorescent molecules in the solid state. As a generalizable strategy, we show that prior to material synthesis, the cargo can be encapsulated into the protein nanocages using a dis- and reassembly approach. Toward this end, a new ligand system for gold nanoparticles enables efficient encapsulation of these particles into the nanocages. The gold nanoparticle-loaded protein nanocages are co-assembled with fluorophore-loaded protein nanocages. Binary superlattices are formed because two oppositely charged ferritin nanocages are used as templates for the assembly. The binary crystals show strong exciton-plasmon coupling between the encapsulated fluorophores and gold nanoparticles, which was spatially resolved with fluorescence lifetime imaging. The strategy outlined here offers a modular approach toward binary nanomaterials with highly ordered building blocks.

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A strong light-matter interaction is highly desirable from the viewpoint of both fundamental research and practical application. Here, we propose a dielectric-metal hybrid nanocavity composed of a silicon (Si) nanoparticle and a thin gold (Au) film and investigate numerically and experimentally the coupling between the plasmons supported by the nanocavity and the excitons in an embedded tungsten disulfide (WS2) monolayer. When a Si/WS2/Au nanocavity is excited by the surface plasmon polariton generated on the surface of the Au film, greatly enhanced plasmon-exciton coupling originating from the hybridization of the surface plasmon polariton, the mirror-image-induced magnetic dipole, and the exciton modes is clearly revealed in the angle- or size-resolved scattering spectra. A Rabi splitting as large as ∼240 meV is extracted by fitting the experimental data with a coupled harmonic oscillator model containing three oscillators. Our findings open new horizons for constructing nanoscale photonic devices by exploiting dielectric-metal hybrid nanocavities.

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Dye-dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting and detecting optoelectronic applications. This review elaborates how to tailor these properties of organic semiconductors for organic solar cells (OSCs) and organic photodiodes (OPDs). While these devices rely on similar materials, the demands for their optical properties are rather different, the former requiring a broad absorption spectrum spanning from the UV over visible up to the near-infrared region and the latter an ultra-narrow absorption spectrum at a specific, targeted wavelength. In order to design organic semiconductors satisfying these demands, fundamental insights on the relationship of optical properties are provided depending on molecular packing arrangement and the resultant electronic coupling thereof. Based on recent advancements in the theoretical understanding of intermolecular interactions between slip-stacked dyes, distinguishing classical J-aggregates with predominant long-range Coulomb coupling from charge transfer (CT)-mediated or -coupled J-aggregates, whose red-shifts are primarily governed by short-range orbital interactions, is suggested. Within this framework, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength-selective OPDs, providing important insights into the rational design of thin-film optoelectronic materials.