Diindeno-Fused Dibenzo[a,h]anthracene and Dibenzo[c,l]chrysene: Syntheses,Structural Analyses,and Properties

Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔE_T−S (2.44 kcal mol⁻¹), a small HOMO–LUMO gap (1.06 eV), a wide photoabsorption range (250–1172 nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO–LUMO gap and ΔE_T−S than its helical isomer diindeno[2,1-f:1′,2′-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties.     

Overview of finite elements simulation of temperature profile to estimate properties of materials 3D-printed by laser powder-bed fusion

Laser powder bed fusion(LPBF),like many other additive manufacturing techniques,offers flexibility in design expected to become a disruption to the manufacturing industry.The current cost of LPBF process does not favor a try-anderror way of research,which makes modelling and simulation a field of superior importance in that area of engineering.In this work,various methods used to overcome challenges in modeling at different levels of approximation of LPBF process are reviewed.Recent efforts made towards a reliable and computationally effective model to simulate LPBF process using finite element(FE)codes are presented.A combination of ray-tracing technique,the solution of the radiation transfer equation and absorption measurements has been used to establish an analytical equation,which gives a more accurate approximation of laser energy deposition in powder-substrate configuration.When this new analytical energy deposition model is used in in FE simulation,with other physics carefully set,it enables us to get reliable cooling curves and melt track morphology that agree well with experimental observations.The use of more computationally effective approximation,without explicit topological changes,allows to simulate wider geometries and longer scanning time leading to many applications in real engineering world.Different applications are herein presented including:prediction of printing quality through the simulated overlapping of consecutive melt tracks,simulation of LPBF of a mixture of materials and estimation of martensite inclusion in printed steel.     

An unprecedented transformation mode in aluminium oxazoline-amido-phenolate complexes

This paper describes the effect of solvent-induced synthetic routes of aluminium pendant oxazoline-amido-phenolate complexes. Treatment of ligand precursor L with AlMe₃ in a 1:1 ratio in diethyl ether yielded the four-coordinated complex (LAlMe)₂. Reaction of ligand precursor L with AlMe₃ in a 1:2 ratio in hexane generated the four-coordinated complex L(AlMe₂)₂. A novel transformation mode occurred from L(AlMe₂)₂ to (LAlMe)₂ when using diethyl ether or tetrahydrofuran as solvent. A density functional theory computational study also supports a plausible mechanism. All results were supported by spectroscopic data and in agreement with single-crystal X-ray diffraction structural analysis.     

A Cation and Anion Dual Doping Strategy for the Elevation of Titanium Redox Potential for High-Power Sodium-Ion Batteries

Titanium-based polyanions have been intensively investigated for sodium-ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti-based cathodes of Na₃Ti_0.5V_0.5(PO₃)₃N as a new cathode material for sodium ion batteries. Both the Ti³⁺/Ti⁴⁺ and V³⁺/V⁴⁺ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near-zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron-based X-ray diffraction. First-principles calculations reveal its well-interconnected 3D Na diffusion pathways with low energy barriers, and the two-sodium-extracted intermediate NaTi_0.5V_0.5(PO₃)₃N is also a stable phase according to formation energy calculations.     

Visible-Light-Induced Heptacene Generation under Ambient Conditions: Utilization of Single-crystal Interior as an Isolated Reaction Site

The photo-induced generation of unstable molecules generally requires stringent conditions to prevent oxidation and the concomitant decomposition of the products. The visible-light-induced conversion of two heptacene precursors to heptacene was studied. Single crystals of bis- and mono-α-diketone-type heptacene precursors ( 7-DK2 and 7-DK1 , respectively), were prepared to investigate the effect of precursor structure on reactivity. The photoirradiation of a 7-DK2 single crystal cleaved only one α-diketone group, forming an intermediate bearing a pentacene subunit, while that of a 7-DK1 single crystal gave rise to characteristic absorption peaks of heptacene and their increase in intensity with photoirradiation time, indicating the generation of heptacene without decomposition. Heptacene production was not observed when the precursors were photoirradiated in solution, implying that the single crystal interior provided isolation from the external environment, thus preventing heptacene oxidation.     

Nonlinear frequency response analysis: a recent review and perspectives

The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them.     

Self-Assembled Monolayers of Bi-Functionalized Porphyrins: A Novel Class of Hole-Layer-Coordinating Perovskites and Indium Tin Oxide in Inverted Solar Cells

Self-assembled monolayers (SAMs) offer the advantage of facile interfacial modification, leading to significant improvements in device performance. In this study, we report the design and synthesis of a new series of carboxylic acid-functionalized porphyrin derivatives, namely AC-1, AC-3, and AC-5, and present, for the first time, a strategy to exploit the large π-moiety of porphyrins as a backbone for interfacing the indium tin oxide (ITO) electrode and perovskite active layer in an inverted perovskite solar cell (PSC) configuration. The electron-rich nature of porphyrins facilitates hole transfer and the formation of SAMs, resulting in a dense surface that minimizes defects. Comprehensive spectroscopic and dynamic studies demonstrate that the double-anchored AC-3 and AC-5 enhance SAMs on ITO, passivate the perovskite layer, and function as conduits to facilitate hole transfer, thus significantly boosting the performance of PSCs. The champion inverted PSC employing AC-5 SAM achieves an impressive solar efficiency of 23.19 % with a high fill factor of 84.05 %. This work presents a novel molecular engineering strategy for functionalizing SAMs to tune the energy levels, molecular dipoles, packing orientations to achieve stable and efficient solar performance. Importantly, our comprehensive investigation has unraveled the associated mechanisms, offering valuable insights for future advancements in PSCs.     

Two‐dimensional reactive scattering with transmitted quantum trajectories

A simple and easy‐to‐implement method is presented for the study of time‐dependent reaction dynamics by propagating an ensemble of transmitted quantum trajectories. During the trajectory evolution, reflected trajectories are gradually removed and all the remaining trajectories represent the transmitted subensemble. The removal process of reflected trajectories avoids numerical instabilities arising from node formation in the reactant region, and allows stable long‐time propagation of transmitted trajectories. This method is applied to a two‐dimensional model chemical reaction. Excellent computational results are obtained for the time‐dependent reaction probabilities evaluated by the time integration of the probability flux. © 2014 Wiley Periodicals, Inc.     

On the Dual Phosphorescence of Xanthone and Chromone in Glassy Hydrocarbon Hosts

Trace quantities of hydrogen‐bonding impurities in otherwise highly purified and dried glassy hydrocarbon matrices at 77 K can modify the relative triplet state energy levels, and hence the photophysical properties of two aromatic ketones, xanthone and chromone, to the extent that the intrinsic spectroscopic properties are obscured. The intrinsic spectroscopic properties of each are revealed in multicrystalline n‐alkane Shpol'skii matrices, and also can be observed in rigorously purified and dried hydrocarbon glasses at 77 K. The extreme sensitivity to stoichiometric, and even substoichiometric quantities of hydrogen‐bonding impurities arises from the near‐degeneracy of the two lowest‐lying triplet states, and the sensitive nature of the n→π* blueshift phenomena to specific hydrogen‐bonding interactions.