Heteropolynuclear complexes of 3,5-dimethylpyrazolate [Pt2M4(Me2pz)8] (M = Ag, Cu). Highly luminescent character of the triplet excited state based on mixed-metal cores

The platinum dimer and heteropolynuclear platinum complexes of 3,5-dimethylpyrazolate, [Pt2M4(mu-Me2pz)8] [M = H (1), Ag (2), Cu (3)], were synthesized and structurally characterized. They exhibit yellow, sky-blue, and orange luminescence, respectively, in the solid state. The absorption bands of 2 and 3 are mainly assigned to the combination of the metal-metal-to-ligand charge-transfer and [Pt2 --> Pt2M4] transitions by the time-dependent density functional theory (DFT) method. DFT calculations also indicate that the emissive states of 2 and 3 are 3[Pt2 --> Pt2Ag4] and 3[Cu(d) --> Pt2Cu4], respectively.     

Cover Feature: Fluoroalkyl Sulfoximines for Versatile Photocatalytic Radical Fluoroalkylations (Chem. Rec. 9/2023)

Fluoroalkyl sulfoximines, which serve as electron-accepting fluoroalkyl radical sources, are easy-to-handle, solid, and bench-stable chemicals. Fluoroalkyl radicals can be generated from sulfoximine reagents using strong one-electron injectors, such as a highly reducing photoredox catalyst in the excited state. Our group has developed photocatalytic radical di- and mono-fluoromethylation and α-monofluoroalkylation of olefins with the corresponding fluoroalkyl sulfoximines. In this personal account, appropriate combinations of fluoroalkyl sulfoximines and photoredox catalysts, leading to successful radical fluoroalkylation, have been discussed.     

Unraveling Inter‐ and Intrachain Electronics in Polythiophene Assemblies Mediated by Coordination Nanospaces

Strong interchain interactions render unsubstituted polythiophene un‐fusible, non‐melting, and insoluble. Therefore, control of the packing structure, which has a profound effect on the optical and electronic properties of the polymer, has never been achieved. Unsubstituted polythiophene was prepared in the one‐dimensional channels of [La(1,3,5‐benzenetrisbenzoate)]_n, where polymer chains form unprecedented assembly structures mediated by the host framework. It is noteworthy that the emission and carrier transport properties were drastically changed by varying the number of chains within a particular assembly. The response of the composite to additional guests is also examined as a method to use the composites as low‐concentration sensors. Our findings show that the encapsulation of polymer chains in host materials is a facile method for understanding the intrinsic properties of conjugated polymers, along with controlling and enhancing their functions.     

Charge‐Transfer Phase Transition of a Cyanide‐Bridged FeII/FeIII Coordination Polymer

Heterometallic Prussian blue analogues are known to exhibit thermally induced charge transfer, resulting in switching of optical and magnetic properties. However, charge‐transfer phase transitions have not been reported for the simplest FeFe cyanide‐bridged systems. A mixed‐valence Fe^II/Fe^III cyanide‐bridged coordination polymer, {[Fe(Tp)(CN)₃]₂Fe(bpe)?5 H₂O}_n, which demonstrates a thermally induced charge‐transfer phase transition, is described. As a result of the charge transfer during this phase transition, the high‐spin state of the whole system does not change to a low‐spin state. This result is in contrast to FeCo cyanide‐bridged systems that exhibit charge‐transfer‐induced spin transitions.     

Identification of HcgC as a SAM‐Dependent Pyridinol Methyltransferase in [Fe]‐Hydrogenase Cofactor Biosynthesis

Previous retrosynthetic and isotope‐labeling studies have indicated that biosynthesis of the iron guanylylpyridinol (FeGP) cofactor of [Fe]‐hydrogenase requires a methyltransferase. This hypothetical enzyme covalently attaches the methyl group at the 3‐position of the pyridinol ring. We describe the identification of HcgC, a gene product of the hcgA‐G cluster responsible for FeGP cofactor biosynthesis. It acts as an S‐adenosylmethionine (SAM)‐dependent methyltransferase, based on the crystal structures of HcgC and the HcgC/SAM and HcgC/S‐adenosylhomocysteine (SAH) complexes. The pyridinol substrate, 6‐carboxymethyl‐5‐methyl‐4‐hydroxy‐2‐pyridinol, was predicted based on properties of the conserved binding pocket and substrate docking simulations. For verification, the assumed substrate was synthesized and used in a kinetic assay. Mass spectrometry and NMR analysis revealed 6‐carboxymethyl‐3,5‐dimethyl‐4‐hydroxy‐2‐pyridinol as the reaction product, which confirmed the function of HcgC.     

Metal‐Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent‐Iodine‐Promoted Oxidative C−C Bond Formation

The enantioselective oxyarylation of (E)‐6‐aryl‐1‐silyloxylhex‐3‐ene was achieved using a lactate‐based chiral hypervalent iodine(III) reagent in the presence of boron trifluoride diethyl etherate. The silyl ether promotes the oxidative cyclization, and enhances the enantioselectivity. In addition, the corresponding aminoarylation was achieved.     

Thermally Induced Intra‐Carboxyl Proton Shuttle in a Molecular Rack‐and‐Pinion Cascade Achieving Macroscopic Crystal Deformation

Proton transport via dynamic molecules is ubiquitous in chemistry and biology. However, its use as a switching mechanism for properties in functional molecular assemblies is far less common. In this study, we demonstrate how an intra‐carboxyl proton shuttle can be generated in a molecular assembly akin to a rack‐and‐pinion cascade via a thermally induced single‐crystal‐to‐single‐crystal phase transition. In a triply interpenetrated supramolecular organic framework (SOF), a 4,4′‐azopyridine (azpy) molecule connects to two biphenyl‐3,3′,5,5′‐tetracarboxylic acid (H₄BPTC) molecules to form a functional molecular system with switchable mechanical properties. A temperature change reversibly triggers a molecular movement akin to a rack‐and‐pinion cascade, which mainly involves 1) an intra‐carboxyl proton shuttle coupled with tilting of the azo molecules and azo pedal motion and 2) H₄BPTC translation. Moreover, both the molecular motions are collective, and being propagated across the entire framework, leading to a macroscopic crystal expansion and contraction.     

Palladium-catalyzed direct arylation of aryl(azaaryl)methanes with aryl halides providing triarylmethanes

Direct arylation of aryl(azaaryl)methanes with aryl halides takes place at the benzylic position in the presence of a hydroxide base under palladium catalysis to yield triarylmethanes.