Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

Path integral quantization corresponding to the deformed Heisenberg algebra

In this paper, the deformation of the Heisenberg algebra, consistent with both the generalized uncertainty principle and doubly special relativity, has been analyzed. It has been observed that, though this algebra can give rise to fractional derivative terms in the corresponding quantum mechanical Hamiltonian, a formal meaning can be given to them by using the theory of harmonic extensions of function. Depending on this argument, the expression of the propagator of the path integral corresponding to the deformed Heisenberg algebra, has been obtained. In particular, the consistent expression of the one dimensional free particle propagator has been evaluated explicitly. With this propagator in hand, it has been shown that, even in free particle case, normal generalized uncertainty principle and doubly special relativity show very much different result.     

Transition‐Metal‐Free Trifluoromethylthiolation of N‐Heteroarenes

A general and efficient methodology for the direct transition metal free trifluoromethylthiolation of a broad range of biologically relevant N‐heteroarenes is reported employing abundant sodium chloride as the catalyst. This method is operationally simple, exhibits high functional group tolerance, and does not require protecting groups.     

D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers

The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed.     

Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Immobilized Catalysts for Iridium‐Catalyzed Allylic Amination: Rate Enhancement by Immobilization

The first immobilized catalyst for Ir‐catalyzed asymmetric allylic aminations is described. The catalyst is a cationic (π‐allyl)Ir complex bound by cation exchange to an anionic silica gel support. Preparation of the catalyst is facile, and the supported catalyst displayed considerably enhanced activity compared with the parent homogeneous catalyst. Up to 43 consecutive amination runs were possible in recycling experiments.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.