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Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M+ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li+, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO2 into CO. Chemical reduction of alkali cations to their metals is extremely challenging. Here, the authors synthesized a series of redox-active borate anions stabilized by bipyridine ligands which can reduce lithium ions generating elemental lithium metal and borate radicals. [ABSTRACT FROM AUTHOR]

Efficient saturated red and near‐infrared (NIR) emissive materials are needed in the development of organic light‐emitting diodes (OLEDs), with applications extending beyond flat panel displays and lighting luminaries. Toward this aim, a series of bis‐tridentate Ir(III) complexes (3a ‒ 3c and 4a ‒ 4c) are designed and synthesized, showing emission spanning the region of 601‒694 nm in degassed toluene. Their emission tuning is mainly achieved using monoanionic chromophoric chelates, L1H for red and L2H for deep‐red and NIR, where the extended π‐conjugation and electron deficient N atoms are introduced synergistically. Moreover, three ancillary chelates, X1H2, X2H2, and X3H2, delivered a secondary influence via varied donor strength to the central Ir(III) atom. The resulting red and deep‐red OLED devices exhibit maximum (max.) external quantum efficiencies (EQEs) of 21.4% and 18.1% with peak maximum at 620 and 666 nm, respectively. More impressively, the device based on 4b delivers a NIR emission peak maximum at 702 nm with a maximum EQE of 10.0%. [ABSTRACT FROM AUTHOR]

The report concerns expansion of the previously developed M-[O,N,C] [pyridine-2-phenolate-6-(σ-aryl)] catalyst system into rigid, coplanar bimetallic assemblies, which afford metal–metal distances that are predetermined yet amenable for cooperativity, as well as locked-in "syn" orientation of binding sites that offer the same direction of access for substrates. The binuclear complexes are generated in a regioselective manner to yield para hydrogen atoms (not ortho) at the central μ-aryl moiety, and have been characterised by multinuclear NMR spectroscopy. The "anti" (showing opposite directions of access) and mononuclear analogues have also been prepared for comparison purposes. Six syn-type bimetallic derivatives of Ti, Zr and Hf have been characterised by X-ray crystallography, to reveal metal–metal separations of 6.3–6.7 Å. For ethylene and ethylene/1-octene polymerisation reactions in conjunction with trityl borate, the syn-Ti2 catalysts display superior efficiencies and produced polymers with higher Mw values than for the anti and mono-Ti congeners, thus indicating the possibility of favourable enchainment interactions and cooperative reactivity. [ABSTRACT FROM AUTHOR]

Ir(III) based carbene complexes are highly sought after in the field of organic light-emitting diodes (OLEDs), as they are expected to solve the thorny issue of efficient and durable blue phosphors. Hence, three tris-bidentate Ir(III) based carbene complexes, namely, f-ct4a–c , were synthesized and fully characterized by both spectroscopic and structural methods, presenting a bulky 2,6-dimethylphenyl substituent on the imidazo[4,5-b]pyrazin-2-ylidene fragment, and a distinctive N-aryl (i.e., either phenyl or 4-t-butylphenyl) appendage and cyclometalating group. These complexes exhibited sky-blue emission with a peak max. located between 473 and 482 nm and a photoluminescent quantum yield (PLQY) of 50–68% recorded in degassed toluene, and furthermore, a much-improved PLQY of 71–87% upon doping in the 2,8-bis(diphenylphosphoryl)dibenzo[b,d]thiophene (PPT) host matrix. Remarkably, the f-ct4b based OLED device and respective hyper-OLED device exhibited blue Commission Internationale de L'Eclairage CIEx,y coordinates of (0.19,0.47) and (0.11,0.44), and max. external quantum efficiencies (EQEs) of 17.4% and 21.5%, respectively, demonstrating their potential in future OLED applications. [ABSTRACT FROM AUTHOR]

Platinum‐based complexes are among the most widely utilized cancer therapeutics. Current Pt(II) drugs face some challenges including toxicity and drug resistance. To solve these issues, great efforts have been devoted to developing nonclassical platinum complexes, such as Pt(IV) prodrugs, that act via mechanisms distinct from those of the approved drugs. Compared with active Pt(II) counterparts, Pt(IV) complexes are relatively inert. Although direct interactions between Pt(IV) complexes and nucleotides have been reported, the reaction is slow due to the kinetic inertness of Pt(IV) complexes. Herein, we design and synthesize a Pt(IV) monotrifluoromethyl complex, in which the chloride ligand that is trans to trifluoromethyl ligand is reactive. The Pt(IV) monotrifluoromethyl complex is very stable in water but displays high reactivity towards various substrates including buffer components and 5'‐dGMP. The study of reaction mechanism reveals that this Pt(IV) complex reacts with phosphate via SN2 nucleophilic substitution pathway, which is different from Pt(II) drugs. The Pt(IV) monotrifluoromethyl complex is cytotoxic in human ovarian cancer cells. Our work reports an example of a reactive organometallic Pt(IV) complex that can directly interact with nucleophiles and implies its potential as an anticancer agent. [ABSTRACT FROM AUTHOR]