Encapsulating Semiconductor Quantum Dots in Supramolecular Cages Enables Ultrafast Guest-Host Electron and Vibrational Energy Transfer.

In the field of supramolecular chemistry, host-guest systems have been extensively explored to encapsulate a wide range of substrates, owing to emerging functionalities in nanoconfined space that cannot be achieved in dilute solutions. However, host-guest chemistry is still limited to encapsulation of small guests. Herein, we construct a water-soluble metallo-supramolecular hexagonal prism with a large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto the building blocks. Then, assembled prisms are able to encapsulate quantum dots (QDs) with diameters of less than 5.0 nm. Furthermore, we find that the supramolecular cage around each QD strongly modifies the photophysics of the QD by universally increasing the rates of QD relaxation processes via ultrafast electron and vibrational energy transfer. Taken together, these efforts expand the scope of substrates in host-guest systems and provide a new approach to tune the optical properties of QDs.

Mapping Simulated Two-Dimensional Spectra to Molecular Models Using Machine Learning.

Two-dimensional (2D) spectroscopy encodes molecular properties and dynamics into expansive spectral data sets. Translating these data into meaningful chemical insights is challenging because of the many ways chemical properties can influence the spectra. To address the task of extracting chemical information from 2D spectroscopy, we study the capacity of simple feedforward neural networks (NNs) to map simulated 2D electronic spectra to underlying physical Hamiltonians. We examined hundreds of simulated 2D spectra corresponding to monomers and dimers with varied Franck-Condon active vibrations and monomer-monomer electronic couplings. We find the NNs are able to correctly characterize most Hamiltonian parameters in this study with an accuracy above 90%. Our results demonstrate that NNs can aid in interpreting 2D spectra, leading from spectroscopic features to underlying effective Hamiltonians.

π-Stacking-Dependent Vibronic Couplings Drive Excited-State Dynamics in Perylenediimide Assemblies.

Vibronic coupling, the interplay of electronic and nuclear vibrational motion, is considered a critical mechanism in photoinduced reactions such as energy transfer, charge transfer, and singlet fission. However, our understanding of how particular vibronic couplings impact excited-state dynamics is lacking due to the limited number of experimental studies of model molecular systems. Herein, we use two-dimensional electronic spectroscopy (2DES) to launch and interrogate a range of vibronic coherences in two distinct types of perylenediimide slip stacks─along the short and long molecular axes, which form either an excimer or a mixed state between the Frenkel exciton (FE) and charge transfer states. We explore the functionality of these vibronic coherences using quantum beatmaps, which display the Fourier amplitude signal oscillations as a function of pump and probe frequencies, along with knowledge of the characteristic signatures of the FE, ionic, and excimer species. We find that a low-frequency vibrational mode of the short-axis slip stack appears concomitantly with the formation of the excimer state, survives 2-fold longer than in the FE state in the reference monomer, and shows a phase shift compared to other modes. For the long-axis slip stacks, a pair of low-frequency modes coupled to a high-frequency coordinate of the FE state were found to play a critical role in mixed-state generation. Our findings thus experimentally reveal the complex and varying roles of vibronic couplings in tightly packed multimers undergoing a range of photoinduced processes.

Accelerating symmetry-breaking charge separation in a perylenediimide trimer through a vibronically coherent dimer intermediate.

Understanding the photophysics and photochemistry of molecular π-stacked chromophores is important for utilizing them as functional photonic materials. However, these investigations have been mostly limited to covalent molecular dimers, which can only approximate the electronic and vibronic interactions present in the higher oligomers typical of functional organic materials. Here we show that a comparison of the excited-state dynamics of a covalent slip-stacked perylenediimide dimer (2) and trimer (3) provides fundamental insights into electronic state mixing and symmetry-breaking charge separation (SB-CS) beyond the dimer limit. We find that coherent vibronic coupling to high-frequency modes facilitates ultrafast state mixing between the Frenkel exciton (FE) and charge-transfer (CT) states. Subsequently, solvent fluctuations and interchromophore low-frequency vibrations promote CT character in the coherent FE/CT mixed state. The coherent FE/CT mixed state persists in 2, but, in 3, low-frequency vibronic coupling collapses the coherence, resulting in ultrafast SB-CS between the distal perylenediimide units.

Temperature Tuning of Coherent Mixing between States Driving Singlet Fission in a Spiro-Fused Terrylenediimide Dimer.

The excited-state dynamics of a spiro-fused terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer (sTDI2) in toluene and 2-methyltetrahydrofuran (mTHF) were investigated as a function of temperature using femtosecond- and nanosecond-transient absorption spectroscopy, as well as two-dimensional electronic spectroscopy. The spiro conjugation and the corresponding geometry of this compound guarantee a short intermonomer distance along with a partial orbital overlap between the orthogonal TDI π-electron systems, providing electronic coupling between the TDIs. Photoexcitation of sTDI2 in toluene, a low dielectric solvent, at 295 K, results in the ultrafast formation of a state composed of a coherent mixture of singlet 1(S1S0), multiexciton 1(T1T1), and charge-transfer (CT) electronic characters. This mixed species decays to decorrelated triplet states on the nanosecond timescale, completing the process of intramolecular singlet fission (SF) in sTDI2. Upon decreasing the temperature from 295 to 200 K, the contribution of the 1(T1T1) state to the mixed species decreases concurrently with an increase in the CT state character. We attribute this behavior to the variation in the vibrational energy level alignment between the states comprising the mixture due to changes in the temperature and hence the local dielectric environment. In contrast, photoexcitation of sTDI2 in more polar mTHF at 295 K results in the formation of a mixed singlet and CT state before undergoing symmetry-breaking charge separation, owing to the increased stabilization of the CT state in the medium. However, in glassy mTHF at 85 K, photoexcited sTDI2 exhibits discernible multiexciton character, comparable to that observed in toluene at 200 K, which we rationalize by the similarity of the dielectric constants under these two sets of conditions. These observations of mixed states of varying diabatic contributions over the range of experimental conditions show that the temperature and the static dielectric constant can directly control the composition of the electronically mixed excited state of sTDI2 and thus the fate of the SF process.

Influence of Vibronic Coupling on Ultrafast Singlet Fission in a Linear Terrylenediimide Dimer.

Singlet fission (SF) is a photophysical process capable of boosting the efficiency of solar cells. Recent experimental investigations into the mechanism of SF provide evidence for coherent mixing between the singlet, triplet, and charge transfer basis states. Up until now, this interpretation has largely focused on electronic interactions; however, nuclear motions resulting in vibronic coupling have been suggested to support rapid and efficient SF in organic chromophore assemblies. Further information about the complex interactions between vibronic excited states is needed to understand the potential role of this coupling in SF. Here, we report mixed singlet and correlated triplet pair states giving rise to sub-50 fs SF in a terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer in which the two TDI molecules are covalently linked by a direct N-N connection at one of their imide positions, leading to a linear dimer with perpendicular TDI π systems. We observe the transfer of low-frequency coherent wavepackets between the initial predominantly singlet states to the product triplet-dominated states. This implies a non-negligible dependence of SF on nonadiabatic coupling in this dimer. We interpret our experimental results in the framework of a modified Holstein Hamiltonian, which predicts that vibronic interactions between low-frequency singlet modes and high-frequency correlated triplet pair motions lead to mixing of the pure basis states. These results highlight how nonadiabatic mixing can shape the complex potential energy landscape underlying ultrafast SF.

Spherical Nucleic Acids: Integrating Nanotechnology Concepts into General Chemistry Curricula.

Nanoscience and technology research offer exciting avenues to modernize undergraduate-level General Chemistry curricula. In particular, spherical nucleic acid (SNA) nanoconjugates, which behave as "programmable atom equivalents" (PAEs) in the context of colloidal crystals, are one system that one can use to reinforce foundational concepts in chemistry including matter and atoms, the Periodic Table, Lewis dot structures and the octet rule, valency and valence-shell electron-pair repulsion (VSEPR) theory, and Pauling's rules, ultimately leading to enriching discussions centered on materials chemistry and biochemistry with key implications in medicine, optics, catalysis, and other areas. These lessons connect historical and modern concepts in chemistry, relate course content to current professional and popular science topics, inspire critical and creative thinking, and spur some students to continue their science, technology, engineering, and mathematics (STEM) education and attain careers in STEM fields. Ultimately, and perhaps most importantly, these lessons may expand the pool of young students interested in chemistry by making connections to a broader group of contemporary concepts and technologies that impact their lives and enhance their view of the field. Herein, a way of teaching aspects of General Chemistry in the context of modern nanoscience concepts is introduced to instructors and curricula developers at research institutions, primarily undergraduate institutions, and community colleges worldwide.

Balancing Charge Transfer and Frenkel Exciton Coupling Leads to Excimer Formation in Molecular Dimers: Implications for Singlet Fission.

Photoexcitation of molecular chromophore aggregates can form excimer states that play a significant role in photophysical processes such as charge and energy transfer as well as singlet fission. An excimer state is commonly defined as a superposition of Frenkel exciton and charge transfer states. In this work, we investigate the dynamics of excimer formation and decay in π-stacked 9,10-bis(phenylethynyl)anthracene (BPEA) covalent dimers appended to a xanthene spacer, where the electronic coupling between the two BPEA molecules is adjusted by changing their longitudinal molecular slip distances. Using exciton coupling calculations, we quantify the relative contributions of Frenkel excitons and charge transfer states and find that there is an upper and lower threshold of the charge transfer contribution for efficient excimer formation to occur. Knowing these thresholds can aid the design of molecular aggregates that optimize singlet fission.

Steric Interactions Impact Vibronic and Vibrational Coherences in Perylenediimide Cyclophanes.

Designing molecular systems that exploit vibronic coherence to improve light harvesting efficiencies relies on understanding how interchromophoric interactions, such as van der Waals forces and dipolar coupling, influence these coherences in multichromophoric arrays. However, disentangling these interactions requires studies of molecular systems with tunable structural relationships. Here, we use a combination of two-dimensional electronic spectroscopy and femtosecond stimulated Raman spectroscopy to investigate the role of steric hindrance between chromophores in driving changes to vibronic and vibrational coherences in a series of substituted perylenediimide (PDI) cyclophane dimers. We report significant differences in the frequency power spectra from the cyclophane dimers versus the corresponding monomer reference. We attribute these differences to distortion of the PDI cores from steric interactions between the substituents. These results highlight the importance of considering structural changes when rationalizing vibronic coupling in multichromophoric systems.

Transient Two-Dimensional Electronic Spectroscopy: Coherent Dynamics at Arbitrary Times along the Reaction Coordinate.

Recent advances in two-dimensional electronic spectroscopy (2DES) have enabled identification of fragile quantum coherences in condensed-phase systems near the equilibrium molecular geometry. In general, traditional 2DES cannot measure such coherences associated with photophysical processes that occur at times significantly after the initially prepared state has dephased, such as the evolution of the initial excited state into a charge transfer state. We demonstrate the use of transient two-dimensional electronic spectroscopy (t-2DES) to probe coherences in an electron donor-acceptor dyad consisting of a perylenediimide (PDI) acceptor and a perylene (Per) donor. An actinic pump pulse prepares the lowest excited singlet state of PDI followed by formation of the PDI•--Per•+ ion pair, which is probed at different times following the actinic pulse using 2DES. Analysis of the observed coherences provides information about electronic, vibronic, and vibrational interactions at any time along the reaction coordinate for ion pair formation.

Quantum coherence in ultrafast photo-driven charge separation.

Coherent interactions are prevalent in photodriven processes, ranging from photosynthetic energy transfer to superexchange-mediated electron transfer, resulting in numerous studies aimed towards identifying and understanding these interactions. A key motivator of this interest is the non-statistical scaling laws that result from coherently traversing multiple pathways due to quantum interference. To that end, we employed ultrafast transient absorption spectroscopy to measure electron transfer in two donor-acceptor molecular systems comprising a p-(9-anthryl)-N,N-dimethylaniline chromophore/electron donor and either one or two equivalent naphthalene-1,8:4,5-bis(dicarboximide) electron acceptors at both ambient and cryogenic temperatures. The two-acceptor compound shows a statistical factor of 2.1 ± 0.2 rate enhancement at room temperature and a non-statistical factor of 2.6 ± 0.2 rate enhancement at cryogenic temperatures, suggesting correlated interactions between the two acceptors with the donor and with the bath modes. Comparing the charge recombination rates indicates that the electron is delocalized over both acceptors at low temperature but localized on a single acceptor at room temperature. These results highlight the importance of shielding the system from bath fluctuations to preserve and ultimately exploit the coherent interactions.

Two-Dimensional Electronic Spectroscopy Reveals Excitation Energy-Dependent State Mixing during Singlet Fission in a Terrylenediimide Dimer.

Singlet fission (SF) is a spin-allowed process in which a singlet exciton, 1(S1S0), within an assembly of two or more chromophores spontaneously down-converts into two triplet excitons via a multiexciton correlated triplet pair state, 1(T1T1). To elucidate the involvement of charge transfer (CT) states and vibronic coupling in SF, we performed 2D electronic spectroscopy (2DES) on dilute solutions of a covalently linked, slip-stacked terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer. This dimer undergoes efficient SF in nonpolar 1,4-dioxane and symmetry-breaking charge separation in polar dichloromethane. The various 2DES spectral features in 1,4-dioxane show different pump wavelength dependencies, supporting the presence of mixed states with variable 1(S1S0), 1(T1T1) and CT contributions that evolve with time. Analysis of the 2DES spectra in dichloromethane reveals the presence of a state having largely 1(T1T1) character during charge separation. Therefore, the 1(T1T1) multiexciton state plays an important role in the photophysics of this TDI dimer irrespective of solvent polarity.

Photothermal Effectiveness of Magnetite Nanoparticles: Dependence upon Particle Size Probed by Experiment and Simulation.

The photothermal effect of nanoparticles has proven efficient for driving diverse physical and chemical processes; however, we know of no study addressing the dependence of efficacy on nanoparticle size. Herein, we report on the photothermal effect of three different sizes (5.5 nm, 10 nm and 15 nm in diameter) of magnetite nanoparticles (MNP) driving the decomposition of poly(propylene carbonate) (PPC). We find that the chemical effectiveness of the photothermal effect is positively correlated with particle volume. Numerical simulations of the photothermal heating of PPC supports this observation, showing that larger particles are able to heat larger volumes of PPC for longer periods of time. The increased heating duration is likely due to increased heat capacity, which is why the volume of the particle functions as a ready guide for the photothermal efficacy.