Multichromophoric Systems Research Articles

How Blinking Affects Photon Correlations in Multichromophoric Nanoparticles

A single chromophore can only emit a maximum of one single photon per excitation cycle. This limitation results in a phenomenon commonly referred to as photon antibunching (pAB). When multiple chromophores contribute to the fluorescence measured, the degree of pAB has been used as a metric to "count" the number of chromophores. But the fact that chromophores can switch randomly between bright and dark states also impacts pAB and can lead to incorrect chromophore numbers being determined from pAB measurements. By both simulations and experiment, we demonstrate how pAB is affected by independent and collective chromophore blinking, enabling us to formulate universal guidelines for correct interpretation of pAB measurements. We use DNA-origami nanostructures to design multichromophoric model systems that exhibit either independent or collective chromophore blinking. Two approaches are presented that can distinguish experimentally between these two blinking mechanisms. The first one utilizes the different excitation intensity dependence on the blinking mechanisms. The second approach exploits the fact that collective blinking implies energy transfer to a quenching moiety, which is a time-dependent process. In pulsed-excitation experiments, the degree of collective blinking can therefore be altered by time gating the fluorescence photon stream, enabling us to extract the energy-transfer rate to a quencher. The ability to distinguish between different blinking mechanisms is valuable in materials science, such as for multichromophoric nanoparticles like conjugated-polymer chains as well as in biophysics, for example, for quantitative analysis of protein assemblies by counting chromophores.

Emissive and reactive excimers in a covalently-linked supramolecular multi-chromophoric system with a balanced rigid-flexible structure

A novel multi-chromophoric system, triad, in which two styrylbenzoquinoline (SBQ) photochromes are connected by a balanced rigid-flexible linker comprising 2,3-naphthylene framework (a residue of 3-oxy-2-naphthoic acid) and tetramethylene groups, was designed and synthesized to study an excimer formation in the excited state. The 1H NMR data testified that triad exists in solution as folded conformers with asymmetric parallel-displaced SBQ units. Under light irradiation, in the triad, competitive photoisomerization and [2 + 2] photocycloaddition reactions were observed, both reactions being reversible. The photocycloaddition resulted in a tetrasubstituted cyclobutane. The red-shifted fluorescence spectrum and the appearance of a long-lived component in the triad fluorescence decay indicated formation of an 'emissive' excimer. The photocycloaddition is assumed to occur in a 'reactive' excimer, in which the ethylene groups of the SBQ photochromes are located at a distance sufficient for the formation of the σ-bonds between them. Quantum-chemical density functional theory (DFT) calculations at M06-2X/6-31G* level predicted the existence of the triad conformers with π-stacking interaction of SBQ photochromes, the structure of which is pre-organized for the excimer formation and photocycloaddition. For the first time, both emissive and reactive excimers were experimentally observed in the multi-chromophoric system with two diarylethylene photochromes undergoing [2 + 2] photocycloaddition.

Exciton Diffusion, Antenna Effect, and Quenching Defects in Superficially Dye-Doped Conjugated Polymer Nanoparticles

Energy transfer (ET) in conjugated polymer nanoparticles (CPNs) is a critical process that affects the performance of these materials in diverse applications such as biological–chemical–physical sensing, imaging, photovoltaics, and phototherapy. Herein, we performed an in-depth study of ET in the CPNs of poly(9,9-dioctylfluorene-altbenzothiadiazole) (F8BT) superficially doped with well-controlled amounts of rhodamine B (RhB) dye using a combined experimental and theoretical approach. In these particles, the conjugated polymer acts as the excitation energy donor, whereas adsorbed dye molecules and non-emissive quenching defect sites (Q) act as energy acceptors. Fitting of simulated polymer emission to experimental data provided the intrinsic exciton diffusion length (Ld = 8.6 nm) of the polymer and the mean number of quenching defects per particle (ρQ¯=1.56×10−2defects/nm2). Importantly, results provide for the first time sound evidence indicating that quenching defect centers are superficially, rather than volumetrically, distributed in these CPNs. The so-called antenna effect (AE), a parameter frequently used to characterize the ET process in donor–acceptor multichromophoric systems, was also calculated. The AE in these CPNs takes a maximum value of ∼40, which compares well with the values reported for similar systems. The developed model (and associated computational Python code) represents a significant improvement over previous models/codes by correcting inconsistencies and successfully simulating ET processes in dye-doped CPNs taking into account: exciton diffusion, ET to non-emissive quenching defect centers, ET to dye dopants, spatial distribution of dyes and defects within CPNs, and individual particle excitation probability among other parameters. The model calculates the ensemble-averaged, time-resolved, and time-averaged emission intensity of CPNs and dye dopants for specific CPN size distributions, allowing for direct comparison with experimental bulk measurements. We envisage that the presented improvements in both the theoretical model and the experimental strategy will prove useful in the study and design of new dye-doped CPNs for practical applications.

The Ultrafast Quantum Dynamics of Photoexcited Adenine-Thymine Basepair Investigated with a Fragment-based Diabatization and a Linear Vibronic Coupling Model.

In this contribution we present a quantum dynamical study of the photoexcited hydrogen bonded base pair adenine–thymine (AT) in a Watson–Crick arrangement. To that end, we parametrize Linear Vibronic Coupling (LVC) models with Time-Dependent Density Functional Theory (TD-DFT) calculations, exploiting a fragment diabatization scheme (FrD) we have developed to define diabatic states on the basis of individual chromophores in a multichromophoric system. Wavepacket propagations were run with the multilayer extension of the Multiconfiguration Time-Dependent Hartree method. We considered excitations to the three lowest bright states, a ππ* state of thymine and two ππ* states (La and Lb) of adenine, and we found that on the 100 fs time scale the main decay pathways involve intramonomer population transfers toward nπ* states of the same nucleobase. In AT this transfer is less effective than in the isolated nucleobases, because hydrogen bonding destabilizes the nπ* states. The population transfer to the A → T charge transfer state is negligible, making the ultrafast (femtosecond) decay through the proton coupled electron transfer mechanism unlikely, in line with experimental results in apolar solvents. The excitation energy transfer is also very small. We carefully compare the predictions of LVC Hamiltonians obtained with different sets of diabatic states, defined so to match either local states of the two separated monomers or the base pair adiabatic states in the Franck–Condon region. To that end we also extend the flexibility of the FrD-LVC approach, introducing a new strategy to define fragments diabatic states that account for the effect of the rest of the multichromohoric system through a Molecular Mechanics potential.

Excimers in Multichromophoric Assemblies: Boon or Bane?

Exciton dynamics in organic semiconductors is a subject of great significance from the standpoint of light emission, as well as light harvesting. As transient excited state species, excimers are expected to play a significant role in the dynamics and the fate of the excited state. Till recently, the discourse on excimers in organic systems revolved around their role in aggregation-induced fluorescence quenching, or utilizing their characteristic red-shifted emission to report local interactions. But in the last decade, research in the area of organic multichromophoric systems has brought the spotlight back on this fascinating species. This review focuses on recent developments that highlight the importance of excimers in various processes involving multichromophoric systems, such as circularly polarized emission, exciton migration, and singlet fission. The review also attempts to address the question of whether excimers are useful or detrimental to various photophysical and photochemical processes of importance.Table of content:IntroductionExcimers in Multichromophoric AssembliesExcimer LuminescenceExcimers in Light HarvestingConclusions and Outlook

Electronic Circular Dichroism Spectra of DNA Quadruple Helices Studied by Molecular Dynamics Simulations and Excitonic Calculations including Charge Transfer States.

We here investigate the Electronic Circular Dichroism (ECD) Spectra of two representative Guanine-rich sequences folded in a Quadruple helix (GQ), by using a recently developed fragment diabatisation based excitonic model (FrDEx). FrDEx can include charge transfer (CT) excited states and consider the effect of the surrounding monomers on the local excitations (LEs). When applied to different structures generated by molecular dynamics simulations on a fragment of the human telomeric sequence (Tel21/22), FrDEx provides spectra fully consistent with the experimental one and in good agreement with that provided by quantum mechanical (QM) method used for its parametrization, i.e., TD-M05-2X. We show that the ECD spectrum is moderately sensitive to the conformation adopted by the bases of the loops and more significantly to the thermal fluctuations of the Guanine tetrads. In particular, we show how changes in the overlap of the tetrads modulate the intensity of the ECD signal. We illustrate how this correlates with changes in the character of the excitonic states at the bottom of the and bands, with larger LE and CT involvement of bases that are more closely stacked. As an additional test, we utilised FrDEx to compute the ECD spectrum of the monomeric and dimeric forms of a GQ forming sequence T30695 (5TGGGTGGGTGGGTGGG3), i.e., a system containing up to 24 Guanine bases, and demonstrated the satisfactory reproduction of the experimental and QM reference results. This study provides new insights on the effects modulating the ECD spectra of GQs and, more generally, further validates FrDEx as an effective tool to predict and assign the spectra of closely stacked multichromophore systems.

Reversible Electronic Energy Transfer (Homo-FRET) in Cyclic Molecular and Supramolecular Systems: Fluorescence Anisotropy Decays for the Isotropic Interaction.

Reversible electronic energy transfer (homo-FRET) in cyclic multichromophoric systems is studied for sets of n identical fluorophores arranged in regular polygons (triangle, square, pentagon, etc.). A general analytic expression for the anisotropy decay is obtained for a regular polygon of any order, under the assumptions of isotropic interaction and nearest-neighbor FRET. A graphical way of connecting the decay form and polygon geometry based on the Frost circle is also presented. The consequences of the relaxation of these assumptions on the anisotropy decay are also discussed and analyzed in detail for the heptagon.

Fragment Diabatization Linear Vibronic Coupling Model for Quantum Dynamics of Multichromophoric Systems: Population of the Charge-Transfer State in the Photoexcited Guanine-Cytosine Pair.

We introduce a method (FrD-LVC) based on a fragment diabatization (FrD) for the parametrization of a linear vibronic coupling (LVC) model suitable for studying the photophysics of multichromophore systems. In combination with effective quantum dynamics (QD) propagations with multilayer multiconfigurational time-dependent Hartree (ML-MCTDH), the FrD-LVC approach gives access to the study of the competition between intrachromophore decays, like those at conical intersections, and interchromophore processes, like exciton localization/delocalization and the involvement of charge-transfer (CT) states. We used FrD-LVC parametrized with time-dependent density functional theory (TD-DFT) calculations, adopting either CAM-B3LYP or ωB97X-D functionals, to study the ultrafast photoexcited QD of a guanine-cytosine (GC) hydrogen-bonded pair, within a Watson-Crick arrangement, considering up to 12 coupled diabatic electronic states and the effect of all of the 99 vibrational coordinates. The bright excited states localized on C and, especially, on G are predicted to be strongly coupled to the G → C CT state, which is efficiently and quickly populated after an excitation to any of the four lowest energy bright local excited states. Our QD simulations show that more than 80% of the excited population on G and ∼50% of that on C decay to this CT state in less than 50 fs. We investigate the role of vibronic effects in the population of the CT state and show that it depends mainly on its large reorganization energy so that it can occur even when it is significantly less stable than the bright states in the Franck-Condon region. At the same time, we document that the formation of the GC pair almost suppresses the involvement of dark nπ* excited states in the photoactivated dynamics.

Natural DNA assisted white light generation and stimuli responsive colour tuning

The unique structure of a natural nucleic acid, calf thymus DNA, which can provide an appropriate scaffold for an efficient cascaded energy transfer among organic chromophores, has been used for the generation of bright and pure white light on UV light excitation. Two most commonly used DNA stains, 4′,6-diamidino-2-phenylindole (DAPI) and ethidium bromide (EB) have been used as a part of the donor-acceptor pairs. We have judiciously selected 10-anthracene-10-yl-3-methylbenzothiazol-3-ium chloride (AnMBTZ), an ultrafast molecular rotor, to act as a bridge between DNA bound DAPI and EB for the cascaded flow of energy. The unique molecular rotor properties of AnMBTZ and its exceptional binding ability with natural DNA help to form a distinct tri-chromophoric system in DNA template which can produce bright and pure white light on UV excitation. Detailed flow of energy from photoexcited DAPI to EB via AnMBTZ has been explored using steady state and time-resolved emission spectroscopy. Further, unique binding nature of AnMBTZ with DNA molecules has been used to modulate the colour of the emission from the present tri-chromophoric system by external stimuli, like salt and temperature. Such unique stimuli responsive multi-chromophoric system in a bio-template has great potential for different lightening applications.

Two-dimensional ultrafast transient absorption spectrograph covering deep-ultraviolet to visible spectral region optimized for biomolecules

We report on the implementation of a multi-kHz single-shot referenced non-coherent two-dimensional UV spectrograph based on conventional pump-probe geometry. It has the capability to cover a broad spectral region in excitation from 270-to-380 nm and in the detection from 270-to-390 nm and 320-to-720 nm. Other setups features are: an unprecedented time resolution of 33 fs (standard deviation); signals are photometrically corrected; a single-shot noise of <1 mOD. It has the capability to operate with sample volumes as small as few μl which is an accomplishment in studying biological or biomimetic systems. To show its performances and potentials, we report two preliminary studies on the photophysics of phenanthrenes hosted in a multichromophoric antenna system and of aromatic amino acids in a blue-copper azurin.

The Role of the Core Attachment Positioning in Triggering Intramolecular Singlet Exciton Fission in Perylene Diimide Tetramers.

Previous studies have proposed that the presence of a flexible π-bridge linker is crucial in activating intramolecular singlet exciton fission (iSEF) in multichromophoric systems. In this study, we report the photophysical properties of three analogous perylene diimide (PDI) dendritic tetramers showing flexible/twisted π-bridged structures with α- and β-substitutions and a rigid/planar structure with a β-fused ring (βC) connection to a benzodithiophene-thiophene (BDT-Th) core. The rigidity and enhanced planarity of βC lead to significant intramolecular charge transfer and triplet formation via an intersystem crossing pathway. Steady-state spectroscopic measurements reveal similar absorption and emission spectra for the α-tetramer and the parent PDI monomer. However, their fluorescence quantum yield is significantly different. The negligible fluorescence yield of the α-tetramer (0.04%) is associated with a competitive nonradiative decay pathway. Indeed, for this twisted compound in a high polar environment, a fast and efficient iSEF with a triplet quantum yield of 124% is observed. Our results show that the α-single-bond connections in the α compound are capable of interrupting the coupling among the PDI units, favoring iSEF. We propose that the formation of the double triplet (1[TT]) state is through a superposition of singlet states known as [S1S0][TT]CT, which has been suggested previously for pentacene derivatives. Using steady-state and time-resolved spectroscopic experiments, we demonstrate that the conformational flexibility of the linker itself is necessary but not sufficient to allow iSEF. For the case of the other twisted tetramer, β, the strong π-π co-facial interactions between the adjacent PDI units in its structure lead to excimer formation. These excimer states trap the singlet excitons preventing the formation of the 1[TT] state, thus inhibiting iSEF.

Molecular Structure, Quantum Coherence, and Solvent Effects on the Ultrafast Electron Transport in BODIPY-C60 Derivatives.

Photoinduced electron transfer in multichromophore molecular systems is defined by a critical interplay between their core unit configuration (donor, molecular bridge, and acceptor) and their system-solvent coupling; these lead to energy and charge transport processes that are key in the design of molecular antennas for efficient light harvesting and organic photovoltaics. Here, we quantify the ultrafast non-Markovian dissipative dynamics of electron transfer in D-π-A molecular photosystems comprising 1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (BODIPY), Zn-porphyrin, fulleropyrrolidine, and fulleroisoxazoline. We find that the stabilization energy of the charge transfer states exhibits a significant variation for different polar (methanol, tetrahydrofuran (THF)) and nonpolar (toluene) environments and determine such sensitivity according to the molecular structure and the electron-vibration couplings that arise at room temperature. For the considered donor-acceptor (D-A) dyads, we show that the stronger the molecule-solvent coupling, the larger the electron transfer rates, regardless of the dyads' electronic coherence properties. We find such coupling strengths to be the largest (lowest) for methanol (toluene), with an electron transfer rate difference of 2 orders of magnitude between the polar and nonpolar solvents. For the considered donor-bridge-acceptor (D-B-A) triads, the molecular bridge introduces an intermediate state that allows the realization of Λ or cascaded-type energy mechanisms. We show that the latter configuration, obtained for BDP-ZnP-[PyrC60] in methanol, exhibits the highest transfer rate of all of the computed triads. Remarkably, and in contrast with the dyads, we show that the larger charge transfer rates are obtained for triads that exhibit prolonged electron coherence and population oscillations.

Picosecond time-resolved photon antibunching measures nanoscale exciton motion and the true number of chromophores

The particle-like nature of light becomes evident in the photon statistics of fluorescence from single quantum systems as photon antibunching. In multichromophoric systems, exciton diffusion and subsequent annihilation occurs. These processes also yield photon antibunching but cannot be interpreted reliably. Here we develop picosecond time-resolved antibunching to identify and decode such processes. We use this method to measure the true number of chromophores on well-defined multichromophoric DNA-origami structures, and precisely determine the distance-dependent rates of annihilation between excitons. Further, this allows us to measure exciton diffusion in mesoscopic H- and J-type conjugated-polymer aggregates. We distinguish between one-dimensional intra-chain and three-dimensional inter-chain exciton diffusion at different times after excitation and determine the disorder-dependent diffusion lengths. Our method provides a powerful lens through which excitons can be studied at the single-particle level, enabling the rational design of improved excitonic probes such as ultra-bright fluorescent nanoparticles and materials for optoelectronic devices.

Quantum Dynamics of Exciton Transport and Dissociation in Multichromophoric Systems.

Due to the subtle interplay of site-to-site electronic couplings, exciton delocalization, nonadiabatic effects, and vibronic couplings, quantum dynamical studies are needed to elucidate the details of ultrafast photoinduced energy and charge transfer events in organic multichromophoric systems. In this vein, we review an approach that combines first-principles parameterized lattice Hamiltonians with accurate quantum dynamical simulations using advanced multiconfigurational methods. Focusing on the elementary transfer steps in organic functional materials, we address coherent exciton migration and creation of charge transfer excitons in homopolymers, notably representative of the poly(3-hexylthiophene) material, as well as exciton dissociation at polymer:fullerene heterojunctions. We emphasize the role of coherent transfer, trapping effects due to high-frequency phonon modes, and thermal activation due to low-frequency soft modes that drive a diffusive dynamics.

“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

The electronic circular dichroism (CD)-silent 2,5-bis(biphen-2-yl)terephthalaldehyde has been used as a sensor (reporter) of chirality for primary amines. The through-space inductor–reporter interactions force a change in the chromophore conformation toward one of the diastereomeric forms. The structure of the reporter, with the terminal flipping biphenyl groups, led to generating Cotton effects in both lower- and higher-energy regions of the ECD spectrum. The induction of an optical activity in the chromophore was due to the cascade point-to-axial chirality transmission mechanism. The reporter system turned out to be sensitive to the subtle differences in the inductor structure. Despite the size of the chiral substituent, the molecular structure of the inductor–reporter systems in the solid-state showed many similarities. The most important one was the tendency of the core part of the molecules to adapt pseudocentrosymmetric conformation. Supported by a weak dispersion and Van der Waals interactions, the face-to-face and edge-to-face interactions between the π-electron systems present in the molecule were found to be responsible for the molecular arrangement in the crystal.

1,1'-Bis(diphenylphosphino)ferrocene Platinum(II) Complexes as a Route to Functionalized Multiporphyrin Systems.

In this study, the cationic complex [PtMe(Me2SO)(dppf)]CF3SO3 (PtFc) (dppf = 1,1′-bis(diphenylphosphino)ferrocene) was exploited as a precursor to functionalize the multi-chromophoric system hexakis(pyridyl-porphyrinato)benzene (1). The final adduct [PtFc]18-1, containing eighteen platinum(II) organometallic [PtMe(dppf)] fragments, was prepared and characterized through UV/Vis absorption, 31P{1H}-NMR spectroscopy, and fluorescence emission. UV/vis and fluorescence titrations confirmed the coordination between the platinum(II) center and all the pyridyl moieties of the peripheral substituent groups of the porphyrin. The drop casting of diluted dichloromethane solution of [PtFc]18-1 onto a glass surface afford micrometer-sized emissive porphyrin rings.

Blueish-white-light-emitting Nanographenes Developed by Pd-catalyzed Suzuki-Miyaura Cross Coupling Reactions

Abstract Top-down methods produce nanographenes with many carboxy groups on their edges. These functional groups can be utilized for developing multichromophoric systems. As proof of concept, pyrene is installed on the edges by Pd-catalyzed cross-coupling reactions. The lack of monomer emissions from the functionalized nanographenes indicates that the neighboring chromophores are sufficiently distant to form the excimer. The pyrene-installed nanographene emits bluish-white-light. Its lipophilic nature allows fabricating a nanographene-dispersed polymethyl methacrylate film emitting visible light.

Excitonic Model for Strongly Coupled Multichromophoric Systems: The Electronic Circular Dichroism Spectra of Guanine Quadruplexes as Test Cases.

We here propose a general and flexible approach, based on fragment diabatization, which incorporates charge transfer states and significantly increases the reliability of excitonic Hamiltonians for systems where the chromophores are very close. This model (FrDEx) is used to compute the electronic circular dichroism and absorption spectra of two prototype guanine-rich DNA sequences folded in quadruple helices (GQs), i.e., a fragment of the human telomeric sequence (Tel21, antiparallel), and (TGGGGT)4 (TG4T, parallel). Calculations on different subsets of Tel21 and TG4T, from dimers to tetramers, show that FrDEx provides spectra close to the reference full quantum mechanical (QM) ones (obtained with time-dependent density functional theory), with significant improvements with respect to "standard" excitonic Hamiltonians. Furthermore, these tests enable the most cost-effective procedure for the whole GQ to be determined. FrDEx spectra of Tel21 and TG4T are also in good agreement with the QM and experimental ones and give access to interesting insights into the chemical-physical effects modulating the spectral signals. FrDEx could be profitably used to investigate many other biological and nanotechnological materials, from DNA to (opto)electronic polymers.

Benzanthrone dyes as mediators of cascade energy transfer in insulin amyloid fibrils

Amyloid fibrils, a specific type of protein aggregates, involved in the development of a number of human disorders, currently attract a growing interest in biomedical and nanotechnological aspects. Recently, we demonstrated that amyloid assemblies may serve as a molecular framework for the multi-step Förster resonance energy transfer (msFRET) in the system containing the classical amyloid marker Thioflavin T (ThT) as the primary donor, the phosphonium mediator dye TDV, and the squaraine dye SQ1 as the terminal acceptor. In the present study we extended our efforts towards evaluating the possibility of using novel benzanthrone dyes as mediators of msFRET in the insulin amyloid fibrils. The four-chromophore systems: ThT → the 3-substituted benzanthrone derivative (BA) → the squaraine SQ4 → the squaraine SQ1 were designed to select the most effective mediators among a series of benzanthrones including the 3-methoxybenzanthrone (MBA) and its amino- (ABM, A6, A8) and amidino- (AM1, AM2) derivatives. The FRET efficiencies and the enhancement of SQ1 fluorescence in the fibrillar and non-aggregated insulin were compared to assess the suitability of the employed cascade system for amyloid fibril detection. The possible fibril binding sites for the examined dyes were defined based on the molecular docking studies. It is assumed that amyloid-scaffolded multichromophoric systems can be used in nanophotonic devices.

Imidazoporphyrins with appended polycyclic aromatic hydrocarbons: To conjugate or not to conjugate?

Herein we report the synthesis and characterization of a series of new dyads – imidazo-fused Ni(II) porphyrinates, containing polycyclic aromatic hydrocarbons (PAH) at the C-2 position of the imidazole ring, including pyrene – 1Pyr, anthracene – 1An, and diphenylanthracene – 1Ph2An. Electronic communication between the tetrapyrrolic macrocycles and PAH moieties was comprehensively studied by UV–Vis and fluorescence spectra together with quantum-chemical modelling. DFT calculations, including geometry optimization and analysis of the frontier orbitals, has revealed the efficient conjugation of pyrene and anthracene with porphyrin π-system, while 1Ph2An dyad possessed two isolated non-conjugated π-systems. Interestingly, these conclusions could not be unambiguously ruled out of UV–Vis spectroscopy data alone. Finally, the presence or absence of conjugation was confirmed using the analysis of ellipticities of bond critical points, thus proving this method to be a convenient tool to study the conjugation in multichromophoric porphyrin-based systems.