Conformational and environmental effects on the electronic and vibrational properties of dyes for solar cell devices.

The main challenge for solar cell devices is harvesting photons beyond the visible by reaching the red-edge (650-780 nm). Dye-sensitized solar cell (DSSC) devices combine the optical absorption and the charge separation processes by the association of a sensitizer as a light-absorbing material (dye molecules, whose absorption can be tuned and designed) with a wide band gap nanostructured semiconductor. Conformational and environmental effects (i.e., solvent, pH) can drastically influence the photophysical properties of molecular dyes. This study proposes a combined experimental and computational approach for the comprehensive investigation of the electronic and vibrational properties of a unique class of organic dye compounds belonging to the family of red-absorbing dyes, known as squaraines. Our focus lies on elucidating the intricate interplay between the molecular structure, vibrational dynamics, and optical properties of squaraines using state-of-the-art density functional theory calculations and spectroscopic techniques. Through systematic vibrational and optical analyses, we show that (i) the main absorption peak in the visible range is influenced by the conformational and protonation equilibria, (ii) the solvent polarity tunes the position of the UV-vis absorption, and (iii) the vibrational spectroscopy techniques (infrared and Raman) can be used as informative tools to distinguish between different conformations and protonation states. This comprehensive understanding offers valuable insights into the design and optimization of squaraine-based DSSCs for enhanced solar energy conversion efficiency.

Coherent Vibrations Promote Charge-Transfer across a Graphene-Based Interface.

Discerning the impact of the coherent motion of the nuclei on the timing and efficiency of charge transfer at the donor-acceptor interface is essential for designing performance-enhanced optoelectronic devices. Here, we employ an experimental approach using photocurrent detection in coherent multidimensional spectroscopy to excite a donor aromatic macrocycle and collect the charge transferred to a 2D acceptor layer. For this purpose, we prepared a cobalt phthalocyanine-graphene (CoPc-Gr) interface. Unlike blends, the well-ordered architecture achieved through the physical separation of the two layers allows us to unambiguously collect the electrical signal from graphene alone and associate it with a microscopic understanding of the whole process. The CoPc-Gr interface exhibits an ultrafast electron-transfer signal, stemming from an interlayer mechanism. Remarkably, the signal presents an oscillating time evolution modulated by coherent vibrations originating from the laser-excited CoPc states. By performing Fourier analysis on the beatings and correlating it with the Raman features, along with a comprehensive first-principles characterization of the vibrational coupling in the CoPc excited states, we successfully identify both the orbitals and molecular vibrations that promote the charge transfer at the interface.

Two-Dimensional Electronic Spectroscopy Characterization of Fucoxanthin-Chlorophyll Protein Reveals Excitonic Carotenoid-Chlorophyll Interactions.

Fucoxanthin Chlorophyll Protein (FCP) is a Light Harvesting Complex found in diatoms and brown algae. It is particularly interesting for its efficiency in capturing the blue-green part of the light spectrum due to the presence of specific chromophores (fucoxanthin, chlorophyll a, and chlorophyll c). Recently, the crystallographic structure of FCP was solved, revealing the 3D arrangement of the pigments in the protein scaffold. While this information is helpful for interpreting the spectroscopic features of FCP, it has also raised new questions about the potential interactions between fucoxanthin and chlorophyll c. These interactions were suggested by their spatial closeness but have never been experimentally observed. To investigate this possible interaction mechanism, in this work, two-dimensional electronic spectroscopy (2DES) has been applied to study the ultrafast relaxation dynamics of FCP. The experiments captured an instantaneous delocalization of the excitation among fucoxanthin and chlorophyll c, suggesting the presence of a non-negligible coupling between the chromophores.

Coherent and Incoherent Ultrafast Dynamics in Colloidal Gold Nanorods.

The study of the mechanisms that control the ultrafast dynamics in gold nanoparticles is gaining more attention, as these nanomaterials can be used to create nanoarchitectures with outstanding optical properties. Here pump-probe and two-dimensional electronic spectroscopy have been synergistically employed to investigate the early ultrafast femtosecond processes following photoexcitation in colloidal gold nanorods with low aspect ratio. Complementary insights into the coherent plasmonic dynamics at the femtosecond time scale and incoherent hot electron dynamics over picosecond time scales have been obtained, including important information on the different sensitivity to the pump fluence of the longitudinal and transverse plasmons and their different contributions to the photoinduced broadening and shift.

Molecularly Detailed View of Strong Coupling in Supramolecular Plexcitonic Nanohybrids.

Plexcitons constitute a peculiar example of light-matter hybrids (polaritons) originating from the (strong) coupling of plasmonic modes and molecular excitations. Here we propose a fully quantum approach to model plexcitonic systems and test it against existing experiments on peculiar hybrids formed by Au nanoparticles and a well-known porphyrin derivative, involving the Q branch of the organic dye absorption spectrum. Our model extends simpler descriptions of polaritonic systems to account for the multilevel structure of the dyes, spatially varying interactions with a given plasmon mode, and the simultaneous occurrence of plasmon-molecule and intermolecular interactions. By keeping a molecularly detailed view, we were able to gain insights into the local structure and individual contributions to the resulting plexcitons. Our model can be applied to rationalize and predict energy funneling toward specific molecular sites within a plexcitonic assembly, which is highly valuable for designing and controlling chemical transformations in the new polaritonic landscapes.

Identification of Design Principles for the Preparation of Colloidal Plexcitonic Materials.

Colloidal plexcitonic materials (CPMs) are a class of nanosystems where molecular dyes are strongly coupled with colloidal plasmonic nanoparticles, acting as nanocavities that enhance the light field. As a result of this strong coupling, new hybrid states are formed, called plexcitons, belonging to the broader family of polaritons. With respect to other families of polaritonic materials, CPMs are cheap and easy to prepare through wet chemistry methodologies. Still, clear structure-to-properties relationships are not available, and precise rules to drive the materials' design to obtain the desired optical properties are still missing. To fill this gap, in this article, we prepared a dataset with all CPMs reported in the literature, rationalizing their design by focusing on their three main relevant components (the plasmonic nanoparticles, the molecular dyes, and the capping layers) and identifying the most used and efficient combinations. With the help of statistical analysis, we also found valuable correlations between structure, coupling regime, and optical properties. The results of this analysis are expected to be relevant for the rational design of new CPMs with controllable and predictable photophysical properties to be exploited in a vast range of technological fields.

Time-Frequency Signatures of Electronic Coherence of Colloidal CdSe Quantum Dot Dimer Assemblies Probed at Room Temperature by Two-Dimensional Electronic Spectroscopy.

Electronic coherence signatures can be directly identified in the time-frequency maps measured in two-dimensional electronic spectroscopy (2DES). Here, we demonstrate the theory and discuss the advantages of this approach via the detailed application to the fast-femtosecond beatings of a wide variety of electronic coherences in ensemble dimers of quantum dots (QDs), assembled from QDs of 3 nm in diameter, with 8% size dispersion in diameter. The observed and computed results can be consistently characterized directly in the time-frequency domain by probing the polarization in the 2DES setup. The experimental and computed time-frequency maps are found in very good agreement, and several electronic coherences are characterized at room temperature in solution, before the extensive dephasing due to the size dispersion begins. As compared to the frequency-frequency maps that are commonly used in 2DES, the time-frequency maps allow exploiting electronic coherences without additional post-processing and with fewer 2DES measurements. Towards quantum technology applications, we also report on the modeling of the time-frequency photocurrent response of these electronic coherences, which paves the way to integrating QD devices with classical architectures, thereby enhancing the quantum advantage of such technologies for parallel information processing at room temperature.

Unveiling the impact of the light-source and steric factors on [2+2] heterocycloaddition reactions.

Information gained from in-depth mechanistic investigations can be used to control the selectivity of reactions, leading to the expansion of the generality of synthetic processes and the discovery of new reactivity. Here, we investigate the mechanism of light-driven [2+2] heterocycloadditions (Paternò-Büchi reactions) between indoles and ketones to develop insight into these processes. Using ground-state UV-Vis absorption and transient absorption spectroscopy (TAS), together with DFT calculations, we found that the reactions can proceed via an exciplex or electron-donor-acceptor (EDA) complex, which are key intermediates in determining the stereoselectivity of the reactions. We used this discovery to control the diastereoselectivity of the reactions, gaining access to previously inaccessible diastereoisomeric variants. When moving from 370 to 456 nm irradiation, the EDA complex is increasingly favoured, and the diastereomeric ratio (d.r.) of the product moves from >99:<1 to 47:53. In contrast, switching from methyl to ipropyl substitution favours the exciplex intermediate, reversing the d.r. from 89:11 to 16:84. Our study shows how light and steric parameters can be rationally used to control the diastereoselectivity of photoreactions, creating mechanistic pathways to previously inaccessible stereochemical variants.

The Role of H-Bonds in the Excited-State Properties of Multichromophoric Systems: Static and Dynamic Aspects.

Given their importance, hydrogen bonds (H-bonds) have been the subject of intense investigation since their discovery. Indeed, H-bonds play a fundamental role in determining the structure, the electronic properties, and the dynamics of complex systems, including biologically relevant materials such as DNA and proteins. While H-bonds have been largely investigated for systems in their electronic ground state, fewer studies have focused on how the presence of H-bonds could affect the static and dynamic properties of electronic excited states. This review presents an overview of the more relevant progress in studying the role of H-bond interactions in modulating excited-state features in multichromophoric biomimetic complex systems. The most promising spectroscopic techniques that can be used for investigating the H-bond effects in excited states and for characterizing the ultrafast processes associated with their dynamics are briefly summarized. Then, experimental insights into the modulation of the electronic properties resulting from the presence of H-bond interactions are provided, and the role of the H-bond in tuning the excited-state dynamics and the related photophysical processes is discussed.

Ultrafast Coherent Delocalization Revealed in Multilayer QDs under a Chiral Potential.

In recent years, it was found that current passing through chiral molecules exhibits spin preference, an effect known as Chiral Induced Spin Selectivity (CISS). The effect also enables the reduction of scattering and therefore enhances delocalization. As a result, the delocalization of an exciton generated in the dots is not symmetric and relates to the electronic and hole excited spins. In this work utilizing fast spectroscopy on hybrid multilayered QDs with a chiral polypeptide linker system, we probed the interdot chiral coupling on a short time scale. Surprisingly, we found strong coherent coupling and delocalization despite having long 4-nm chiral linkers. We ascribe the results to asymmetric delocalization that is controlled by the electron spin. The effect is not measured when using shorter nonchiral linkers. As the system mimics light-harvesting antennas, the results may shed light on a mechanism of fast and efficient energy transfer in these systems.

Photoelectrochemical C-H Activation Through a Quinacridone Dye Enabling Proton-Coupled Electron Transfer.

Dye-sensitized photoanodes for C-H activation in organic substrates are assembled by vacuum sublimation of a commercially available quinacridone (QNC) dye in the form of nanosized rods onto fluorine-doped tin oxide (FTO), TiO2 , and SnO2 slides. The photoanodes display extended absorption in the visible range (450-600 nm) and ultrafast photoinduced electron injection (<1 ps, as revealed by transient absorption spectroscopy) of the QNC dye into the semiconductor. The proton-coupled electron-transfer reactivity of QNC is exploited for generating a nitrogen-based radical as its oxidized form, which is competent in C-H bond activation. The key reactivity parameter is the bond-dissociation free energy (BDFE) associated with the N⋅/N-H couple in QNC of 80.5±2.3 kcal mol-1 , which enables hydrogen atom abstraction from allylic or benzylic C-H moieties. A photoelectrochemical response is indeed observed for organic substrates characterized by C-H bonds with BDFE below the 80.5 kcal mol-1 threshold, such as γ-terpinene, xanthene, or dihydroanthracene. This work provides a rational, mechanistically oriented route to the design of dye-sensitized photoelectrodes for selective organic transformations.

Ultrafast Dynamics of Multiple Plexcitons in Colloidal Nanomaterials: The Mediating Action of Plasmon Resonances and Dark States.

Plexcitons, that is, mixed plasmon-exciton states, are currently gaining broad interest to control the flux of energy at the nanoscale. Several promising properties of plexcitonic materials have already been revealed, but the debate about their ultrafast dynamic properties is still vibrant. Here, pump-probe spectroscopy is used to characterize the ultrafast dynamics of colloidal nanohybrids prepared by coupling gold nanoparticles and porphyrin dyes, where one or two sets of plexcitonic resonances can be selectively activated. We found that these dynamics are strongly affected by the presence of a reservoir of states including plasmon resonances and dark states. The time constants regulating the plexciton relaxations are significantly longer than the typical values found in the literature and can be modulated over more than 1 order of magnitude, opening possible interesting perspectives to modify rates of chemically relevant molecular processes.

The Energy Transfer Yield between Carotenoids and Chlorophylls in Peridinin Chlorophyll a Protein Is Robust against Mutations.

The energy transfer (ET) from carotenoids (Cars) to chlorophylls (Chls) in photosynthetic complexes occurs with almost unitary efficiency thanks to the synergistic action of multiple finely tuned channels whose photophysics and dynamics are not fully elucidated yet. We investigated the energy flow from the Car peridinin (Per) to Chl a in the peridinin chlorophyll a protein (PCP) from marine algae Amphidinium carterae by using two-dimensional electronic spectroscopy (2DES) with a 10 fs temporal resolution. Recently debated hypotheses regarding the S2-to-S1 relaxation of the Car via a conical intersection and the involvement of possible intermediate states in the ET were examined. The comparison with an N89L mutant carrying the Per donor in a lower-polarity environment helped us unveil relevant details on the mechanisms through which excitation was transferred: the ET yield was conserved even when a mutation perturbed the optimization of the system thanks to the coexistence of multiple channels exploited during the process.

Engineering the Aggregation of Dyes on Ligand-Shell Protected Gold Nanoparticles to Promote Plexcitons Formation.

The ability to control the light-matter interaction in nanosystems is a major challenge in the field of innovative photonics applications. In this framework, plexcitons are promising hybrid light-matter states arising from the strong coupling between plasmonic and excitonic materials. However, strategies to precisely control the formation of plexcitons and to modulate the coupling between the plasmonic and molecular moieties are still poorly explored. In this work, the attention is focused on suspensions of hybrid nanosystems prepared by coupling cationic gold nanoparticles to tetraphenyl porphyrins in different aggregation states. The role of crucial parameters such as the dimension of nanoparticles, the pH of the solution, and the ratio between the nanoparticles and dye concentration was systematically investigated. A variety of structures and coupling regimes were obtained. The rationalization of the results allowed for the suggestion of important guidelines towards the control of plexcitonic systems.

Supramolecular BODIPY based dimers: synthesis, computational and spectroscopic studies.

The synthetic procedures for the preparation of supramolecular BODIPY dimers decorated with complementary patterns able to induce the formation of a triple hydrogen bond through mutual interactions are here reported. The BODIPY and styryl-equipped BODIPY species have been suitably functionalized in meso position with 2,6-diacetamido-4-pyridyl and 1-butyl-6-uracyl moieties. Dimers and monomers have been subjected to computational and photophysical investigations in solvent media. Various peculiarities concerning the effects of the interaction geometry on the stability of the H-bonded systems have also been investigated. The combination of modelling and experimental data provides a paradigm for improving and refining the BODIPY synthetic pathway to have chromophoric architectures with a programmable supramolecular identity. Furthermore, the possibility of assembling dimers of different dyes through H-bonds could be appealing for a systematic investigation of the principal factors affecting the dynamics of the energy migration and possibly driving coherent transfer mechanisms. Our work highlights how the chemical versatility of these dyes can be exploited to design new BODIPY-based supramolecular architectures.

2D Electronic Spectroscopic Techniques for Quantum Technology Applications.

2D electronic spectroscopy (2DES) techniques have gained particular interest given their capability of following ultrafast coherent and noncoherent processes in real-time. Although the fame of 2DES is still majorly linked to the investigation of energy and charge transport in biological light-harvesting complexes, 2DES is now starting to be recognized as a particularly valuable tool for studying transport processes in artificial nanomaterials and nanodevices. Particularly meaningful is the possibility of assessing coherent mechanisms active in the transport of excitation energy in these materials toward possible quantum technology applications. The diverse nature of these new target samples poses significant challenges and calls for a critical rethinking of the technique and its different realizations. With the confluence of promising new applications and rapidly developing technical capabilities, the enormous potential of 2DES techniques to impact the field of nanosystems, quantum technologies, and quantum devices is here delineated.

Solvent-Dependent Characterization of Fucoxanthin through 2D Electronic Spectroscopy Reveals New Details on the Intramolecular Charge-Transfer State Dynamics.

The electronic state manifolds of carotenoids and their relaxation dynamics are the object of intense investigation because most of the subtle details regulating their photophysics are still unknown. In order to contribute to this quest, here, we present a solvent-dependent 2D Electronic Spectroscopy (2DES) characterization of fucoxanthin, a carbonyl carotenoid involved in the light-harvesting process of brown algae. The 2DES technique allows probing its ultrafast relaxation dynamics in the first 1000 fs after photoexcitation with a 10 fs time resolution. The obtained results help shed light on the dynamics of the first electronic state manifold and, in particular, on an intramolecular charge-transfer state (ICT), whose photophysical properties are particularly elusive given its (almost) dark nature.

Photocurrent-Detected 2D Electronic Spectroscopy Reveals Ultrafast Hole Transfer in Operating PM6/Y6 Organic Solar Cells.

The performance of nonfullerene-acceptor-(NFA)-based organic solar cells is rapidly approaching the efficiency of inorganic cells. The chemical versatility of NFAs extends the light-harvesting range to the infrared, while preserving a considerably high open-circuit-voltage, crucial to achieve power-conversion efficiencies >17%. Such low voltage losses in the charge separation process have been attributed to a low-driving-force and efficient exciton dissociation. Here, we address the nature of the subpicosecond dynamics of electron/hole transfer in PM6/Y6 solar cells. While previous reports focused on active layers only, we developed a photocurrent-detected two-dimensional spectroscopy to follow the charge transfer in fully operating devices. Our measurements reveal an efficient hole-transfer from the Y6-acceptor to the PM6-donor on the subpicosecond time scale. On the contrary, at the same time scale, no electron-transfer is seen from the donor to the acceptor. These findings, putting ultrafast spectroscopy in action on operating optoelectronic devices, provide insight for further enhancing NFA solar cell performance.

Selective switching of multiple plexcitons in colloidal materials: directing the energy flow at the nanoscale.

Coupling of molecular emitters to plasmon resonances in metal nanostructures has long been investigated to control the light-matter interaction at the nanoscale. The emergence of different coupling behaviors can be governed by the various combinations of emitters and plasmonic substrates, as well as the spatial arrangement of the individual components. Here colloidal assembly methods are exploited to prepare a responsive nanosystem where two sets of plexcitonic resonances in different coupling regimes can be selectively switched on and off, acting on external conditions such as concentration and presence of anions. The two sets of plexciton resonances are built exploiting the strong coupling between cationic gold nanoparticles and the same molecular moiety, an anionic porphyrin, in different aggregation states. When both plexciton resonances are simultaneously activated in the system, evidence for a plexciton relaxation cascade has been found in photoluminescence experiments. These findings have fundamental implications for achieving control over energy flow at the nanoscale.