Enantioselective Paternò-Büchi Reactions: Strategic Application of a Triplet Rebound Mechanism for Asymmetric Photocatalysis.

The Paternò-Büchi reaction is the [2 + 2] photocycloaddition of a carbonyl with an alkene to afford an oxetane. Enantioselective catalysis of this classical photoreaction, however, has proven to be a long-standing challenge. Many of the best-developed strategies for asymmetric photochemistry are not suitable to address this problem because the interaction of carbonyls with Brønsted or Lewis acidic catalysts can alter the electronic structure of their excited state and divert their reactivity toward alternate photoproducts. We show herein that a triplet rebound strategy enables the stereocontrolled reaction of an excited-state carbonyl compound in its native, unbound state. These studies have resulted in the development of the first highly enantioselective catalytic Paternò-Büchi reaction, catalyzed by a novel hydrogen-bonding chiral Ir photocatalyst.

A Lead-Free Ferroelectric 2D Dion-Jacobson Tin Iodide Perovskite.

2D hybrid organic-inorganic halide perovskites emerge as a new class of 2D semiconductors with the potential to combine excellent optoelectronic properties with symmetry-enabled properties such as ferroelectricity. Although many lead-based ferroelectric 2D halide perovskites are reported, there is yet to be a conclusive report of ferroelectricity in tin-based 2D perovskites. Here, the structures and properties of a new series of 2D Dion-Jacobson (DJ) Sn perovskites: (4AMP)SnI4, (4AMP)(MA)Sn2I7, and (4AMP)(FA)Sn2I7 (4AMP = 4-(aminomethyl)piperidinium, MA = methylammonium, and FA = formamidinium), are reported. Structural characterization reveals that (4AMP)SnI4 is polar with in-plane spontaneous polarization whereas (4AMP)(MA)Sn2I7 and (4AMP)(FA)Sn2I7 are centrosymmetric. Further, (4AMP)SnI4 displays second harmonic generation (SHG) and polarization-electric field hysteresis measurements confirm it is ferroelectric with a spontaneous polarization of 10.0 µC cm-2 at room temperature. (4AMP)SnI4 transitions into a centrosymmetric structure above 367 K. As the first direct experimental observation of the spontaneous ferroelectric polarization of a Sn-based 2D hybrid perovskite, this work opens up environmentally friendly 2D tin halide perovskites for ferroelectricity and other physical property studies.

Direct Probe of Vibrational Fingerprint and Combination Band Coupling.

Vibrational fingerprints and combination bands are a direct measure of couplings that control molecular properties. However, most combination bands possess small transition dipoles. Here we use multiple, ultrafast coherent infrared pulses to resolve vibrational coupling between CH3CN fingerprint modes at 918 and 1039 cm-1 and combination bands in the 2750-6100 cm-1 region via doubly vibrationally enhanced (DOVE) coherent multidimensional spectroscopy (CMDS). This approach provides a direct probe of vibrational coupling between fingerprint modes and near-infrared combination bands of large and small transition dipoles in a molecular system over a large frequency range.

Strategies for phase matching control in a multidimensional Floquet state spectroscopy.

Floquet state spectroscopy is an optical analogue of multiple quantum coherence nuclear magnetic resonance (MQC-NMR). Tunable ultrafast excitation pulses resonantly excite multiple states in a sample to form the Floquet state. The Floquet state emits multiple coherent beams at frequencies and in directions that conserve energy and momenta. The different output beams differ in the time ordering and coherences created by the excitation beams. They correspond to the different methodologies in the NMR family. Isolating a specific beam and monitoring the output intensity as a function of excitation frequencies creates multidimensional spectra containing cross-peaks between coupled states. The frequency range of the multidimensional spectra is limited by phase matching constraints. This paper presents a new, to the best of our knowledge, active phase matching strategy that increases the versatility of multidimensional Floquet state spectroscopy through both longer sample path lengths and larger spectral ranges.

The yaq project: Standardized software enabling flexible instrumentation.

Modern instrumentation development often involves the incorporation of many dissimilar hardware peripherals into a single unified instrument. The increasing availability of modular hardware has brought greater instrument complexity to small research groups. This complexity stretches the capability of traditional, monolithic orchestration software. In many cases, a lack of software flexibility leads creative researchers to feel frustrated, unable to perform experiments they envision. Herein, we describe Yet Another acQuisition (yaq), a software project defining a new standardized way of communicating with diverse hardware peripherals. yaq encourages a highly modular approach to experimental software development that is well suited to address the experimental flexibility needs of complex instruments. yaq is designed to overcome hardware communication barriers that challenge typical experimental software. A large number of hardware peripherals are already supported, with tooling available to expand support. The yaq standard enables collaboration among multiple research groups, increasing code quality while lowering development effort.

Tuning Structure and Excitonic Properties of 2D Ruddlesden-Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations.

The compositional tunability of 2D metal halide perovskites enables exploration of diverse semiconducting materials with different structural features. However, rationally tuning the 2D perovskite structures to target physical properties for specific applications remains challenging, especially for lead-free perovskites. Here, we study the effect of the interplay of the B-site (Ge, Sn, and Pb), A-site (cesium, methylammonium, and formamidinium), and spacer cations on the structure and optical properties of a new series of 2D Ruddlesden-Popper perovskites using the previously unreported spacer cation 4-bromo-2-fluorobenzylammonium (4Br2FBZ). We report eight new crystal structures and study the consequence of varying the B-site (Pb, Sn, Ge) and dimension (n = 1, 2, vs 3D). Dimension strongly influences local distortion and structural symmetry, and the increased octahedral tilting and lone pair effects in Ge perovskites lead to a polar n = 2 perovskite that exhibits second harmonic generation, (4Br2FBZ)2(Cs)Ge2I7. In contrast, the analogous Sn and Pb perovskites remain centrosymmetric, but the B-site metal influences the photoluminescence properties. The Pb perovskites exhibit broad, defect-mediated emission at low temperature, whereas the Sn perovskites show purely excitonic emission over the entire temperature range, but the carrier recombination dynamics depend on dimensionality and dark excitonic states. Wholistic understanding of these differences that arise based on cations and dimensionality can guide the rational materials design of 2D perovskites for targeting physical properties for optoelectronic applications based on the interplay of cations and the connectivity of the inorganic framework.

Photoluminescence, Reflection Contrast, Raman, and Second Harmonic Generation Spectroscopies Spatially Resolve Strain, Alloying, Defects, and Electronic Characteristics of Lateral MX2 Heterostructures.

Lateral heterostructures of two-dimensional (2D) transition metal dichalcogenides offer promise as platforms for a wide variety of applications from exotic physics to environmental control. Further development and study of these heterostructures require characterization methods that assess the quality of the heterostructures. Here, we extend current characterization strategies to create photoluminescence (PL), Raman, reflection contrast, and second harmonic generation (SHG) maps of individual monolayer core-shell WS2-MoS2 lateral heterostructures that were synthesized via water vapor assisted chemical vapor transport. Together, these methods provide the correlations required to resolve the effects of excitons, trions, lattice defects, strain, and alloying. The comparisons show substantial differences, especially in the regions near and at the narrow heterointerface. Comparisons between the different spectral maps show the importance of metal alloying for understanding the electronic and spatial structures of heterostructures. The results are compared to previous work on similar lateral heterostructures created by different methods.

Spatial Heterogeneity of Biexcitons in Two-Dimensional Ruddlesden-Popper Lead Iodide Perovskites.

Quantum confinement in two-dimensional (2D) Ruddlesden-Popper (RP) perovskites leads to the formation of stable quasi-particles, including excitons and biexcitons, the latter of which may enable lasing in these materials. Due to their hybrid organic-inorganic structures and the solution phase synthesis, microcrystals of 2D RP perovskites can be quite heterogeneous, with variations in excitonic and biexcitonic properties between crystals from the same synthesis and even within individual crystals. Here, we employ one- and two-quantum two-dimensional white-light microscopy to systematically study the spatial variations of excitons and biexcitons in microcrystals of a series of 2D RP perovskites BA2MAn-1PbnI3n+1 (n = 2-4, BA= butylammonium, MA = methylammonium). We find that the average biexciton binding energy of around 60 meV is essentially independent of the perovskite layer thickness (n). We also resolve spatial variations of the exciton and biexciton energies on micron length scales within individual crystals. By comparing the one-quantum and two-quantum spectra at each pixel, we conclude that biexcitons are more sensitive to their environments than excitons. These results shed new light on the ways disorder can modify the energetic landscape of excitons and biexcitons in RP perovskites and how biexcitons can be used as a sensitive probe of the microscopic environment of a semiconductor.

X-ray/Extreme Ultraviolet Floquet State Multidimensional Spectroscopy, an Analogue of Multiple Quantum Nuclear Magnetic Resonance.

There is great interest in developing fully coherent multidimensional X-ray/extreme ultraviolet (XUV) spectroscopic techniques because of their capability for achieving atomic spectral selectivity. Current proposals rest on using sequentially and coherently driven core excitations with multiple X-ray/XUV excitation pulses and measuring the output using time domain Fourier transform methods. In this paper, we propose an alternative method that creates an entanglement of core and optical transitions to form a Floquet state that creates directional and coherent output beams. Multidimensional spectra are obtained by measuring the intensity of output beams while tuning the optical frequencies across resonances. This approach expands on previous optical pump-XUV probe spectroscopy of MoTe2 by theoretically demonstrating its multidimensional capabilities. Both parametric and non-parametric pathways are proposed to optimize the resolution of inhomogeneous broadening and k-selective features.

Distinct Carrier Transport Properties Across Horizontally vs Vertically Oriented Heterostructures of 2D/3D Perovskites.

Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)2PbBr4 (PEA = phenylethylammonium) microplates onto 3D CsPbBr3 single crystal thin films, with well-defined heterojunctions. Time-resolved photoluminescence (TRPL) transients of the heterostructures exhibit the monomolecular and bimolecular dynamics expected from exciton annihilation, dissociation, and recombination, as well as evidence for carrier transfer in these heterostructures. Two kinetic models based on Type-I and Type-II band alignments at the interface of horizontal 2D/3D heterostructures are applied to reveal a shift in balance between carrier transfer and recombination: Type-I band alignment better describes the behaviors of heterostructures with thin 2D perovskite microplates but Type-II band alignment better describes those with thick 2D microplates (>150 nm). TRPL of vertically aligned 2D microplates is dominated by directly excited PL and is independent of the height above the 3D film. Electrical measurements reveal current rectification behaviors in both heterostructures with vertical heterostructures showing better electrical transport. As the first systematic study on comparing models of 2D/3D perovskite heterostructures with controlled orientations and compositions, this work provides insights on the charge transfer mechanisms in these perovskite heterostructures and guidelines for designing better optoelectronic devices.

Anion Exchange of Ruddlesden-Popper Lead Halide Perovskites Produces Stable Lateral Heterostructures.

Heterostructures of three-dimensional (3D) halide perovskites are unstable because of facile anion interdiffusion at halide interfaces. Two-dimensional (2D) Ruddlesden-Popper halide perovskites (RPPs) show suppressed and anisotropic ion diffusion that could enable stable RPP heterostructures, yet the direct and general growth of lateral RPP heterostructures remains challenging. Here, we show that halide miscibility in RPPs decreases with perovskite layer thickness (n), enabling the formation of sharp halide lateral heterostructures from n = 1 and 2 RP lead iodide microplates via anion exchange with hydrogen bromide vapor. In contrast, RPPs with n ≥ 3 form more diffuse lateral heterojunctions, more similar to those in 3D perovskites. The anion exchange behaviors are further modulated by the spacer and A-site cations in the RPP structures. These new insights, and kinetic studies of the exchange reactions, enable the preparation of lateral heterostructures from various n = 2 RPPs that are more stable against anion interdiffusion and degradation for potential optoelectronic device applications.

Deterministic fabrication of arbitrary vertical heterostructures of two-dimensional Ruddlesden-Popper halide perovskites.

Ruddlesden-Popper lead halide perovskites have emerged as a new class of two-dimensional semiconductors with tunable optoelectronic properties, potentially offering unlimited heterostructure configurations for exploration. However, the practical realization of such heterostructures is challenging because of the difficulty in achieving controllable direct synthesis or van der Waals integration of halide perovskites due to their mobile and fragile crystal lattices. Here we report direct growth of large-area nanosheets of diverse phase-pure Ruddlesden-Popper perovskites with thicknesses down to one monolayer at the solution-air interface and a reliable approach for gently transferring and stacking these nanosheets. These advances enable the deterministic fabrication of arbitrary vertical heterostructures and multi-heterostructures of Ruddlesden-Popper perovskites with greater structural degrees of freedom that define the electronic structures of the heterojunctions. Such rationally designed heterostructures exhibit interesting interlayer properties, such as interlayer carrier transfer and reduction of the photoluminescence linewidth, and could enable the exploration of exciton physics and optoelectronic applications.

Supertwisted spirals of layered materials enabled by growth on non-Euclidean surfaces.

Euclidean geometry is the fundamental mathematical framework of classical crystallography. Traditionally, layered materials are grown on flat substrates; growing Euclidean crystals on non-Euclidean surfaces has rarely been studied. We present a general model describing the growth of layered materials with screw-dislocation spirals on non-Euclidean surfaces and show that it leads to continuously twisted multilayer superstructures. This model is experimentally demonstrated by growing supertwisted spirals of tungsten disulfide (WS2) and tungsten diselenide (WSe2) draped over nanoparticles near the centers of spirals. Microscopic structural analysis shows that the crystal lattice twist is consistent with the geometric twist of the layers, leading to moiré superlattices between the atomic layers.

Disentangling Second Harmonic Generation from Multiphoton Photoluminescence in Halide Perovskites using Multidimensional Harmonic Generation.

Layered two-dimensional Ruddlesden-Popper (RP) halide perovskites are an intriguing class of semiconductors being explored for their linear and nonlinear optical and ferroelectric properties. Second harmonic generation (SHG) is commonly used to screen for noncentrosymmetric and ferroelectric materials. However, SHG measurements of perovskites can be obscured by their intense multiphoton photoluminescence (mPL). Here, we apply multidimensional harmonic generation as a method to eliminate the complications from mPL. By scanning and correlating both excitation and emission frequencies, we unambiguously assess whether a material supports SHG by examining if an emission feature scales as twice the excitation frequency. Measurements of a series of n = 2, 3 RP perovskites reveal that, contrary to previous belief, n-butylammonium (BA) RP perovskites are not SHG-active and thus centrosymmetric, but RP perovskites with phenylethylammonium (PEA) and 2-thiophenemethylammonium (TPMA) spacer cations display SHG. This work establishes multidimensional harmonic generation as a definitive method to measure SHG in halide perovskites.

Schrödinger Cat State Spectroscopy-A New Frontier for Analytical Chemistry.

The invention of the laser generated great excitement, because its ability to create quantum state coherences could form a new family of coherent spectroscopies that were the optical analogue of multidimensional nuclear magnetic resonance (NMR). The full realization of this promise has not yet been realized, but the pathway forward is clear. The path involves the use of multiple, tunable lasers that create a Schrödinger cat state, where the system is simultaneously in a mixture of vibrational and/or electronic states. The multiplicity of these states confers many advantages for analytical methods: high selectivity from the multiple spectral dimensions, line-narrowing, isolation of spectral features where quantum states are coupled, and spectral decongestion. Now that the feasibility of Schrödinger cat spectroscopy has been demonstrated, the future is open for the development of a new frontier in analytical chemistry that creates a new set of tools for studying the complex systems that form the heart of analytical chemistry.

Conducting Excitation and Emission Spectra in the IR Regime: Frequency-Domain Time-Resolved Vibrational Four Wave Mixing Spectroscopy.

We report new features of recently developed ultrafast coherent multidimensional spectroscopy (CMDS), an optical analogue to multidimensional NMR. By using both frequency- and time-domain nonlinear four wave mixing methods, CMDS is able to directly observe coherence transfer (CT), the coherent quantum mechanical analogue of population relaxation. Using a mixture of acetonitrile and magnesium perchlorate (1.0 M) as a model system, we demonstrated that this one color- and population-involving CT process makes CMDS capable of measuring samples with features that mimic excitation and emission spectral measurements in fluorescence spectroscopy. With the new capabilities, one might develop CMDS into a versatile vibrational tool for revealing the role of coherence as a design element in realizing a function. Furthermore, CT-based vibrational resonance energy transfer (VRET) methods may be developed for label-free biosensing and imaging, such as those demonstrated by fluorescence resonance energy transfer (FRET).

Multicolor Heterostructures of Two-Dimensional Layered Halide Perovskites that Show Interlayer Energy Transfer.

Fabrication of heterostructures using two-dimensional (2D) materials with different bandgaps creates opportunities for exploring new properties and device applications. Ruddlesden-Popper (RP) layered halide perovskites have recently emerged as a new class of solution-processable 2D materials that demonstrate exotic optoelectronic properties. However, heterostructures using 2D halide perovskites have not been achieved. Here, we report a simple solution growth method for making vertically stacked double heterostructures and complex multilayer heterostructures of 2D lead iodide perovskites [(PEA)2(MA) n-1Pb nI3 n+1, PEA = C6H5(CH2)2NH3+, MA = CH3NH3+] via van der Waals epitaxy. These heterostructures present atomically sharp interfaces and display distinct photoluminescence that allow fingerprinting the RP phases. Time-resolved photoluminescence measurements reveal internal energy transfer from higher energy bandgap (lower n value) perovskite layers to lower energy bandgap (higher n value) perovskite layers on the time scale of hundreds of picoseconds due to natural type I band alignments. These results offer new strategies to fabricate perovskite-perovskite heterojunctions by taking advantage of surface-bound ligands as spatial barriers to prevent ion migration across the junctions. These heterostructures capable of multicolor emission with high spectral purity are promising for light-emitting applications.

Three Dimensional Triply Resonant Sum Frequency Spectroscopy Revealing Vibronic Coupling in Cobalamins: Toward a Probe of Reaction Coordinates.

Triply resonant sum frequency (TRSF) spectroscopy is a fully coherent mixed vibrational-electronic spectroscopic technique that is ideally suited for probing the vibrational-electronic couplings that become important in driving reactions. We have used cyanocobalamin (CNCbl) and deuterated aquacobalamin (D2OCbl+) as model systems for demonstrating the feasibility of using the selectivity of coherent multidimensional spectroscopy to resolve electronic states within the broad absorption spectra of transition metal complexes and identify the nature of the vibrational and electronic state couplings. We resolve three short and long axis vibrational modes in the vibrationally congested 1400-1750 cm-1 region that are individually coupled to different electronic states in the 18 000-21 000 cm-1 region but have minimal coupling to each other. Double resonance with the individual vibrational fundamentals and their overtones selectively enhances the corresponding electronic resonances and resolves features within the broad absorption spectrum. This work demonstrates the feasibility of identifying coupling between different pairs of vibrational states with different electronic states that together form the reaction coordinate surface of transition metal enzymes.

Communication: Multidimensional triple sum-frequency spectroscopy of MoS2 and comparisons with absorption and second harmonic generation spectroscopies.

Triple sum-frequency (TSF) spectroscopy is a recently developed methodology that enables collection of multidimensional spectra by resonantly exciting multiple quantum coherences of vibrational and electronic states. This work reports the first application of TSF to the electronic states of semiconductors. Two independently tunable ultrafast pulses excite the A, B, and C features of a MoS2 thin film. The measured TSF spectrum differs markedly from absorption and second harmonic generation spectra. The differences arise because of the relative importance of transition moments and the joint density of states (JDOS). We develop a simple model and globally fit the absorption and harmonic generation spectra to extract the JDOS and the transition moments from these spectra. Our results validate previous assignments of the C feature to a large JDOS created by band nesting.