Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

A high-order full-discretization method using Hermite interpolation for periodic time-delayed differential equations

A high-order full-discretization method(FDM)using Hermite interpolation(HFDM) is proposed and implemented for periodic systems with time delay. Both Lagrange interpolation and Hermite interpolation are used to approximate state values and delayed state values in each discretization step. The transition matrix over a single period is determined and used for stability analysis. The proposed method increases the approximation order of the semidiscretization method and the FDM without increasing the computational time. The convergence, precision, and efficiency of the proposed method are investigated using several Mathieu equations and a complex turning model as examples. Comparison shows that the proposed HFDM converges faster and uses less computational time than existing methods.     

Global Existence of Renormalized Solutions to Entropy-Dissipating Reaction–Diffusion Systems

Archive for Rational Mechanics and Analysis - In the present work we introduce the notion of a renormalized solution for reaction–diffusion systems with entropy-dissipating reactions. We...     

Imaging of the formerly bonded area of individual fibre to fibre joints with SEM and AFM

Besides the determination of the force and the energy needed to break individual fibre to fibre joints, the investigation of the formerly bonded area (FBA) is of essential importance to learn more about the failure mechanisms of fibre–fibre bonds in general. In this study the surfaces of paper fibres and the FBA of fibre–fibre joints after the determination of the breaking force as well as the bonding energy were analysed by means of low voltage scanning electron microscopy and atomic force microscopy. A comparison between the contact zone of fibres broken at different loading rates as well as under cyclic loading showed that there seems to be no significant difference in the appearance of the FBA in these cases. Only minor delamination of the cell wall could be found in the bonding zone, which indicates no mechanical interlocking of fibrils in the bonding zone. Furthermore, it is shown that some glues used for specimen preparation of fibre–fibre bond strength measurement are forming a glue film on the fiber surface and migrate into the bonding region.     

Methane Oxidation over Cu2+/[CuOH]+ Pairs and Site-Specific Kinetics in Copper Mordenite Revealed by Operando Electron Paramagnetic Resonance and UV/Visible Spectroscopy

Cu-exchanged mordenite (MOR) is a promising material for partial CH₄ oxidation. The structural diversity of Cu species within MOR makes it difficult to identify the active Cu sites and to determine their redox and kinetic properties. In this study, the Cu speciation in Cu-MOR materials with different Cu loadings has been determined using operando electron paramagnetic resonance (EPR) and operando ultraviolet-visible (UV/Vis) spectroscopy as well as in situ photoluminescence (PL) and Fourier-transform infrared (FTIR) spectroscopy. A novel pathway for CH₄ oxidation involving paired [CuOH]⁺ and bare Cu²⁺ species has been identified. The reduction of bare Cu²⁺ ions facilitated by adjacent [CuOH]⁺ demonstrates that the frequently reported assumption of redox-inert Cu²⁺ centers does not generally apply. The measured site-specific reaction kinetics show that dimeric Cu species exhibit a faster reaction rate and a higher apparent activation energy than monomeric Cu²⁺ active sites highlighting their difference in the CH₄ oxidation potential.     

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters

The bimetallic, decanuclear Ni₃Ga₇-cluster of the formula [Ni₃(GaTMP)₃(μ²-GaTMP)₃(μ³-GaTMP)] ( 1 , TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2 . Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- ( 2_Di ), tetra- ( 2_Tetra ) and hexahydride species ( 2_Hexa ). The structures of 2_Di and 2_Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.     

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

Direct In Situ Investigation of Milling Reactions Using Combined X‐ray Diffraction and Raman Spectroscopy

The combination of two analytical methods including time‐resolved in situ X‐ray diffraction (XRD) and Raman spectroscopy provides a new opportunity for a detailed analysis of the key mechanisms of milling reactions. To prove the general applicability of our setup, we investigated the mechanochemical synthesis of four archetypical model compounds, ranging from 3D frameworks through layered structures to organic molecular compounds. The reaction mechanism for each model compound could be elucidated. The results clearly show the unique advantage of the combination of XRD and Raman spectroscopy because of the different information content and dynamic range of both individual methods. The specific combination allows to study milling processes comprehensively on the level of the molecular and crystalline structures and thus obtaining reliable data for mechanistic studies.     

Dynamic Inclusion Complexes of Metal Nanoparticles Inside Nanocups

Host–guest inclusion complexes are abundant in molecular systems and of fundamental importance in living organisms. Realizing a colloidal analogue of a molecular dynamic inclusion complex is challenging because inorganic nanoparticles (NPs) with a well‐defined cavity and portal are difficult to synthesize in high yield and with good structural fidelity. Herein, a generic strategy towards the fabrication of dynamic 1:1 inclusion complexes of metal nanoparticles inside oxide nanocups with high yield (>70 %) and regiospecificity (>90 %) by means of a reactive double Janus nanoparticle intermediate is reported. Experimental evidence confirms that the inclusion complexes are formed by a kinetically controlled mechanism involving a delicate interplay between bipolar galvanic corrosion and alloying–dealloying oxidation. Release of the NP guest from the nanocups can be efficiently triggered by an external stimulus.