Quest for a Desolvated Structure Unveils Breathing Phenomena in a MOF Leading to Greener Catalysis in a Solventless Setup: Insights from Combined Experimental and Computational Studies.

The crystal structure of the metal-organic framework (MOF), {Mn2(1,4-bdc)2(DMF)2}n (1) (1,4-bdcH2, 1,4-benzenedicarboxylic acid; DMF, N,N-dimethylformamide), is known for a long time; however, its desolvated structure, {Mn2(1,4-bdc)2}n (1'), is not yet known. The first-principles-based computational simulation was used to unveil the structure of 1' that shows the expansion in the framework, leading to pore opening after the removal of coordinated DMF molecules. We have used 1' that contains open metal sites (OMSs) in the structure in cyanosilylation and CO2 cycloaddition reactions and recorded complete conversions in a solventless setup. The pore opening in 1' allows the facile diffusion of small aldehyde molecules into the channels, leading to complete conversion. The reactions with larger aldehydes, 2-naphthaldehyde and 9-anthracenecarboxaldehyde, also show 99.9% conversions, which are the highest reported until date in solventless conditions. The in silico simulations illustrate that larger aldehydes interact with Mn(II) OMSs on the surfaces, enabling a closer interaction and facilitating complete conversions. The catalyst shows high recyclability, exhibiting 99.9% conversions in the successive reaction cycles with negligible change in the structure. Our investigations illustrate that the catalyst 1' is economical, efficient, and robust and allows reactions in a solventless greener setup, and therefore the catalysis with 1' can be regarded as "green catalysis".

Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics.

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development.

Porous SnO2 nanosheets for room temperature ammonia sensing in extreme humidity.

Gas sensors based on tin dioxide (SnO2) for the detection of ammonia (NH3) have become commercially available for environmental monitoring due to their reactive qualities when exposed to different gaseous pollutants. Nevertheless, their implementation in the medical field has been hindered by certain inherent drawbacks, such as needing to operate at high temperatures, lack of selectivity, unreliable operation under high-humidity conditions, and a lower detection limit. To counter these issues, this study created 2D nanosheets of SnO2 through an optimized solvothermal method. It was found that tuning the precursor solution's pH to either neutral or 14 led to aggregated or distributed, uniform-size nanosheets with a higher crystallinity, respectively. Remarkably, the SnO2 nanosheet sensor (SNS-14) displayed a much lower response to water molecules and specific reactivity to ammonia even when subjected to reducing and oxidizing agents at 25 °C due to the micropores and chemisorbed oxygen on the nanosheets. Furthermore, the SNS-14 was seen to have the highest sensitivity to ammonia at 100 ppm, with rapid response (8 s) and recovery times (55 s) even at a high relative humidity of 70%. Its theoretical detection limit was recorded to be 64 ppt, better than any of the earlier SnO2-based chemiresistive sensors. Its exceptional sensing abilities were credited to its optimal crystallinity, specific surface area, defects, chemisorbed oxygen, and porous structure. NH3-TPD measurements and computational simulations were employed to understand the ammonia interaction with atomistic details on the SnO2 nanosheet surface. A real time breath sensing experiment was simulated to test the efficacy of the sensor. Reaching this advancement is an achievement in bypassing past boundaries of SnO2-centered sensors, making it feasible to detect ammonia with enhanced precision, discrimination, dependability, and velocity for probable usages in medical diagnostics and ecological surveillance.

Utilizing the Undesirable Oxidation of Lead-Free Hybrid Halide Perovskite Nanosheets for Solar-Driven Photocatalytic C(sp3)─H Activation: Unraveling the Serendipity.

Hybrid halide perovskites (HHPs), whose every branch generates intrusiveness, have been utilized in solar cells from a broader perspective. However, the inclusiveness of employing HHP as a photocatalyst is in its initial stage. This study mainly focuses on the unexpected utilization of, so far, undesirable material vacancy-ordered MA2SnBr6 quantum dots synthesized from MASnBr3 nanosheets. Here, the quantum confinement grounded a large blue shift in ultraviolet (UV) and photoluminescence (PL) spectra with a Stokes shift of 420 meV, where the band gap increase is observed as size decreases in MA2SnBr6. Remarkably, MA2SnBr6 exhibits air and moisture stability, better charge transfer, and high oxidation potential compared to MASnBr3. The first-principles-based atomistic computations reveal the strain relaxation in the Sn-Br framework that structurally stabilizes the MA2SnBr6 lattice. Furthermore, the direct band gap and strongly localized valence band edge give rise to a new potential photocatalyst MA2SnBr6 for efficient solar-driven C(sp3)─H activation of cyclohexane and toluene under ambient conditions.

The impact of spatially heterogeneous chemical doping on the electronic properties of CdSe quantum dots: insights from ab initio computation.

The introduction of copper (Cu) impurity in semiconductor CdSe quantum dots (QDs) gives rise to unique photoluminescence (PL) bands exhibiting distinctive characteristics, like broad line width, significant Stokes shift, and complex temporal decay. The atomistic origins of these spectral features are yet to be understood comprehensively. We employed multiple computational techniques to systematically study the impact of the spatial heterogeneity of Cu atoms on the stability and photophysical properties, including the emission linewidth of doped QDs under ambient conditions. The Cu substitution introduces a spin-polarized intragap state, the energetic position of which is strongly dependent on the dopant location and causes spectral broadening in QD ensembles. Furthermore, the dopant dynamics under ambient conditions are significantly influenced by the specific arrangement of Cu within the QDs. The dynamic electronic structures of surface-doped CdSe illustrate more pronounced perturbations and vary the mid-gap state position more drastically than those of the core-doped QDs. Vibronic coupling broadens the photoluminescence peaks associated with the conduction band-to-defect level transition for individual QDs. These insights into the dynamic structure-photophysical property relationship suggest viable approaches, such as tuning the operational temperature and selective co-doping, to enhance the functional performances of doped CdSe QDs strategically.

Composition Dependent Strain Engineering of Lead-Free Halide Double Perovskite: Computational Insights.

The critical photophysical properties of lead-free halide double perovskites (HDPs) must be substantially improved for various applications. In this regard, strain engineering is a powerful tool for enhancing optoelectronic performance with precise control. Here, we employ ab initio simulations to investigate the impact of mild compressive and tensile strains on the photophysics of Cs2AgB'X6 (B' = Sb, Bi; X = Cl, Br) perovskites. Depending on the pnictogen and halide atoms, the band gap and band edge positions of HDPs can be tuned to a significant extent by controlling the applied external strain. Cs2AgSbBr6 has the most substantial strain response under structural perturbations. The subtle electronic interactions among the participating orbitals and the band dispersion at the edge states are enhanced under compressive strain, reducing the carrier effective masses. The exciton binding energies for these Br-based HDPs are in the range 59-78 meV and weaken in the compressed lattices, suggesting improved free carrier generation. Overall, the study emphasizes the potential of lattice strain engineering to boost the photophysical properties of HDPs that can ultimately improve their optoelectronic performance.

Understanding the Effect of Internal Electrostatic Fields Created by Alkaline Earth Metal Ions Poised over Secondary Coordination Sphere of Molecular Iron Complexes.

Understanding the effect of the local electrical field around the reaction center in enzymes and molecular catalysis is an important topic of research. Herein, we explored the electrostatic field exerted by the alkaline earth metal ions (M2+ = Mg2+, Ca2+, Sr2+, and Ba2+) around Fe in FeIII(Cl) complexes by experimental and computational investigations. M2+ coordinated dinuclear FeIII(Cl) complexes (12M) were synthesized and characterized by X-ray crystallography and different spectroscopic techniques. EPR and magnetic moment measurements exhibited the presence of high-spin FeIII centers in the 12M complexes. Electrochemical investigations revealed FeIII/FeII reduction potential values shifted anodically in 12M complexes compared to 1. Likewise, 2p3/2 and 2p1/2 peaks in the XPS data were found to shift positively in the 12M complexes, demonstrating that redox-inactive metal ions make FeIII more electropositive. However, nearly similar λmax values in the UV-vis spectra were observed in 1 and 12M complexes. The first-principles-based computational simulations further revealed the impact of M2+ on stabilizing 3d-orbitals of Fe. The distortion in Laplacian distribution (∇2ρ(r)) of electron density around M2+ also indicates the possibility of having Fe-M interactions in these complexes. The absence of a bond critical point between FeIII and M2+ ions in the 12M complexes indicates dominant through-space interaction between these metal centers. Experimental and computational studies collectively imply that the installation of internal electrostatic fields exerted by M2+ ions in 12M complexes alters the electronic structure of FeIII.

Favoring Product Desorption by a Tailored Electronic Environment of Oxygen Vacancies in SrTiO3 via Cr Doping for Enhanced and Selective Electrocatalytic CO2 to CO Conversion.

The electrochemical CO2 reduction reaction (ECO2RR) into value-added products is crucial to address the herculean task of CO2 mitigation. Several efforts are being made to develop active ECO2RR catalysts, targeting enhanced CO2 adsorption and activation. A rational design of ECO2RR catalysts with a facile product desorption step is seldom reported. Herein, ensuing the Sabatier principle, we report a strategy for an enhanced ECO2RR with a faradaic efficiency of 85% for CO production by targeting the product desorption step. The energy barrier for product desorption was lowered via a tailored electronic environment of oxygen vacancies (Ovac) in Cr-doped SrTiO3. The substitutional doping of Cr3+ for Ti4+ into the SrTiO3 lattice favors the generation of more Ovac and modifies the local electronic environment. Density functional theory analysis evinces the spontaneous dissociation of COOH# intermediates over Ovac and lower CO intermediate binding on Ovac reducing the energy demand for CO release due to Cr doping.

A Rare Cleptoparasitic Bee Tetralonioidella himalayana (Bingham, 1897) (Hymenoptera: Apidae) from India: Review and New Data.

Tetralonioidella Strand 1914 is a very rare apid genus globally, of which only two species, Tetralonioidella himalayana (Bingham, 1897) and Tetralonioidella tricolor (Lieftinck, 1972), are known from India. They are known to be cleptoparasitic on species of Habropoda Smith, 1854 and Elaphropoda Lieftinck, 1966. During hymenopteran survey in Arunachal Pradesh, we encountered Tetralonioidella himalayana (Bingham, 1897) and observed their behavioral regime, which is very poorly known. The identifying characteristics of both male and female, their foraging behavior, floral preference, distribution pattern, and possible host association have been studied. Exclusive floral association and host specialization are potential contributing factors to the rarity of T. himalayana. Such factors may limit the distribution range of the species. A priori sampling resolution with genetic and demographic exploration is required to evaluate the present status of such bee species.

How structural and vibrational features affect optoelectronic properties of non-stoichiometric quantum dots: computational insights.

While stoichiometric quantum dots (QDs) have been well studied, a significant knowledge gap remains in the atomistic understanding of the non-stoichiometric ones, which are predominantly present during the experimental synthesis. Here, we investigate the effect of thermal fluctuations on structural and vibrational properties of non-stoichiometric cadmium selenide (CdSe) nanoclusters: anion-rich (Se-rich) and cation-rich (Cd-rich) using ab initio molecular dynamics (AIMD) simulations. While the excess atoms on the surface fluctuate more for a given QD type, the optical phonon modes are mostly composed of Se atoms dynamics, irrespective of the composition. Moreover, Se-rich QDs have higher bandgap fluctuations compared to Cd-rich QDs, suggesting poor optical properties of Se-rich QDs. Additionally, non-adiabatic molecular dynamics (NAMD) suggests faster non-radiative recombination for Cd-rich QDs. Altogether, this work provides insights into the dynamic electronic properties of non-stoichiometric QDs and proposes a rationale for the observed optical stability and superiority of cation-rich candidates for light emission applications.

Light-Induced Structural Dynamics and Charge Transport in Layered Halide Perovskite Thin Films.

The dynamic nature of the metal halide perovskite lattice upon photoexcitation plays a vital role in their properties. Here we report an observation of light-induced structure dynamics in quasi-2D Ruddlesden-Popper phase perovskite thin films and its impact on the carrier transport properties. By a time-resolved X-ray scattering technique, we observe a rapid lattice expansion upon photoexcitation, followed by a slow relaxation over the course of 100 ns in the dark. Theoretical modeling suggests that the expansion originates from the lattice's thermal fluctuations caused by photon energy deposition. Power dependent optical spectroscopy and photoconductivity indicate that high laser powers triggered a strong local structural disorder, which increased the charge dissociation activation energy that results in localized transport. Our study investigates the impact of laser energy deposition on the lattices and the subsequent carrier transport properties, that are relevant to device operations.

Charge transport in mixed metal halide perovskite semiconductors.

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm2 V-1 s-1. The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

Ring Expansion of Isatins via 1,2-Phospha-Brook Rearrangement: A Route to the Synthesis of 2-Quinolinone-Derived p-Quinone Methides.

A Lewis acid-mediated one-carbon homologation approach to installing a 2-quinolinone core embedded with para-quinone methides, in a high yield of up to 92%, and with high regioselectivity has been developed. Also, post-synthetic modifications, including C-P, C-S, and C-C bond formations, have been demonstrated by the 1,6-addition of suitable nucleophiles. Further, cyclopropanation of 2-quinolinone-embedded p-QM is also demonstrated affording a contiguous quaternary spiro center.

Point Defects in Two-Dimensional Ruddlesden-Popper Perovskites Explored with Ab Initio Calculations.

Two-dimensional Ruddlesden-Popper (RP) halide perovskites stand out as excellent layered materials with favorable optoelectronic properties for efficient light-emitting, spintronic, and other spin-related applications. However, properties often determined by defects are not well understood in these perovskite systems. This work investigates the ground state electronic structure of commonly formed defects in a typical RP perovskite structure by density functional theory. Our study reveals that these 2D perovskites generally retain their defect tolerance with limited perturbation of the electronic structure in the case of neutral-type point defects. In contrast, donor/acceptor defects induce deep midgap states, potentially causing harm to the material's electronic performance. To retain positive intrinsic properties, the halide vacancies and interstitial defects should be avoided. The observed strong electron localization results in trap states and consequently leads to reduced device performance. This understanding can guide experimental efforts that aim for improved 2D halide perovskite-based device performance.

Impact of Bifunctional Ligands on Charge Transfer Kinetics in CsPbBr3-CdSe/CdS/ZnS Nanohybrids.

Mixed dimensional nanohybrids (MDNHs) between zero-dimensional (0D) perovskites and two-dimensional (2D) II-VI semiconductors hold great potential for photonic device applications. An in-depth study to understand the shuttling of charge carriers is carried out utilizing bifunctional ligands such as 4-aminothiophenol (4-ATP), p-aminobenzoic acid, and 6-amino-2-naphthoic acid in the synthesis of MDNHs of CsPbBr3 nanocrystals (NCs) and CdSe/CdS/ZnS core/shell/shell (CSS) nanoplatelets (NPLs). These MDNHs form donor-bridge-acceptor systems, where the electronic interaction is greatly influenced by the nature of ligands. The smaller size and stronger binding affinity of 4-ATP to CSS NPLs lead to a faster rate of charge transfer as compared to other linkers. Electronic structure calculations under the framework of density functional theory (DFT) confirms that in 4-ATP capped CSS NPLs, stronger electronic overlap occurs between CSS NPLs and 4-ATP at the valence band maxima (VBM). Furthermore, Poisson distribution modeling proposes that in 4-ATP linked MDNHs, the number of CSS NPLs around CsPbBr3 NCs is highest.

Induced Chirality in Halide Perovskite Clusters through Surface Chemistry.

Chiroptical properties are of interest for various applications, including structure determination, polarized photodetectors, and spintronics. Inducing chiroptical activity into semiconductors is challenging because of difficulties in creating asymmetric crystal structures. One promising method is to use chirality transfer by deploying chiral organic molecules as capping ligands for nanocrystals. Experimentally, chiral-capped nanocrystals show emergent chiroptical signatures, but the mechanisms for chirality transfer remain unclear. Here we utilize atomistic modeling using time-dependent density functional theory calculations to explore chirality transfer in CsPbX3 (X = Cl, I) clusters capped with chiral diaminocyclohexane (DACH) enantiomers. When DACH enantiomers are bound to the cluster surface, the perovskite optical transitions gain chiral signatures. This observed chirality transfer is best rationalized by chiral molecular dipole-cluster transition dipole coupling. With multiple DACH molecules bound to the cluster surface, anisotropy factors are found to increase proportionally to the surface ligand density, providing mechanistic insight toward improving chiroptical functionality in semiconductor nanomaterials.

Cesium-Coated Halide Perovskites as a Photocathode Material: Modeling Insights.

Photocathodes emit electrons when illuminated, a process utilized across many technologies. Cutting-edge applications require a set of operating conditions that are not met with current photocathode materials. Meanwhile, halide perovskites have been studied extensively and have shown a lot of promise for a wide variety of optoelectronic applications. Well-documented halide perovskite properties such as inexpensive growth techniques, improved carrier mobility, low trap density, and tunable direct band gaps make them promising candidates for next-generation photocathode materials. Here, we use density functional theory to explore the possible application of pure inorganic perovskites (CsPbBr3 and CsPbI3) as photocathodes. It is determined that the addition of a Cs coating improved the performance by lowering the work function anywhere between 1.5 and 3 eV depending on the material, crystal surface, and surface coverage. A phenomenological model, modified from that developed by Gyftopoulos and Levine, is used to predict the reduction in work function with Cs coverage. The results of this work aim to guide the further experimental development of Cs-coated halide perovskites for photocathode materials.

Excited-State Properties of Defected Halide Perovskite Quantum Dots: Insights from Computation.

CsPbBr3 quantum dots (QDs) have been recently suggested for their application as bright green light-emitting diodes (LEDs); however, their optical properties are yet to be fully understood and characterized. In this work, we utilize time-dependent density functional theory to analyze the ground and excited states of the CsPbBr3 clusters in the presence of various low formation energy vacancy defects. Our study finds that the QD perovskites retain their defect tolerance with limited perturbance to the simulated UV-vis spectra. The exception to this general trend is that Br vacancies must be avoided, as they cause molecular orbital localization, resulting in trap states and lower LED performance. Blinking will likely still plague CsPbBr3 QDs, given that the charged defects critically perturb the spectra via red-shifting and lower absorbance. Our study provides insight into the tunability of CsPbBr3 QDs optical properties by understanding the nature of the electronic excitations and guiding improved development for high-performance LEDs.

Hot Carrier Cooling and Recombination Dynamics of Chlorine-Doped Hybrid Perovskite Single Crystals.

Controlling the photoexcited properties and behavior of hybrid perovskites by halide doping has the potential to impact a wide range of emerging technologies, including solar cells and radiation detectors. Crystalline samples of methylammonium lead bromide substituted with chlorine (MAPbBr3-xClx) were examined by transient reflectivity spectroscopy and nonadiabatic molecular dynamics simulations. At picosecond time scales, the addition of chlorine to the perovskite crystal increased the observed rate of hot carrier cooling and the calculated electron-phonon coupling constants. Chlorine-doped samples also exhibit a slower surface recombination velocity and a smaller ambipolar mobility.

Role of the Metal-Semiconductor Interface in Halide Perovskite Devices for Radiation Photon Counting.

Halide perovskites are promising optoelectronic semiconductors. For applications in solid-state detectors that operate in low photon flux counting mode, blocking interfaces are essential to minimize the dark current noise. Here, we investigate the interface between methylammonium lead tri-iodide (MAPbI3) single crystals and commonly used high and low work function metals to achieve photon counting capabilities in a solid-state detector. Using scanning photocurrent microscopy, we observe a large Schottky barrier at the MAPbI3/Pb interface, which efficiently blocks dark current. Moreover, the shape of the photocurrent profile indicates that the MAPbI3 single-crystal surface has a deep fermi level close to that of Au. Rationalized by first-principle calculations, we attribute this observation to the defects due to excess iodine on the surface underpinning emergence of deep band-edge states. The photocurrent decay profile yields a charge carrier diffusion length of 10-25 µm. Using this knowledge, we demonstrate a single-crystal MAPbI3 detector that can count single γ-ray photons by producing sharp electrical pulses with a fast rise time of <2 µs. Our study indicates that the interface plays a crucial role in solid-state detectors operating in photon counting mode.