Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (∼350 devices), fast switching (≤30 ns), excellent endurance (∼10 cycles), stability (>10 s) and scalability (down to ∼60 nm). In situ Raman and ultraviolet-visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.

Synthesis, characterization, and catalytic alkyne polymerization results for the first trianionic pincer alkylidyne complex, [(t)BuOCO]W≡CC(CH(3))(3)(THF)(2) (6), are described. Complex 6 is a highly active catalyst for the polymerization of acetylenes and exhibits a high turnover number (4371), activity (1.05 × 10(6) g(PPA) mol(cat)(-1) h(-1)),and yield (87%) for the polymerization of 1-ethynyl-4-fluorobenzene.

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This report describes the synthesis and characterization of 1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate (3((1,5))). The synthesis of the dinuclear complex 3((1,5)) is achieved via an unprecedented inorganic click (iClick) reaction between the metal-azide PPh(3)AuN(3) (1) and the metal-acetylide PPh(3)Au-C≡CPh (2). Characterization of 3((1,5)) includes multinuclear NMR spectroscopy, combustion analysis, and single crystal X-ray crystallography. Experimental characterization is complemented with density-functional-theory (DFT) calculations which indicate the 1,4-isomer 3((1,4)) is less stable by 3.3 kcal mol(-1). The energetic difference lies primarily in the ability of the phenyl group in the 4-position of 3((1,5)) to lie coplanar with the triazolate to create a delocalized π-bonding HOMO orbital.

The synthesis, isolation, and metalation of the trianionic PrNCNLi 3 ] 2 (2) is described. The terdentate coordination ability of 2 is demonstrated in the synthesis of the hafnium dichloride anion [2,6-i PrNCNHfCl 2 ]-[Li(DME) 3 ] (3-DME). Complex 3-DME is distorted square pyramidal in the solid state, but NMR eVidence indicates the complex is fluxional and trigonal bypyramidal in solution. Straightforward ligand modification proVides the additional trianionic pincer ligand [3,5-MeNCNLi 2 ] 2 [Li 2 (DME) 6 ] ( 5). This sterically smaller ligand leads to the hafnium pincerate dianion complex [(3, 2 Hf][Li 2 (DME) 2 ] ( 6), which contains two trianionic pincer ligands. The new compounds are characterized by elemental analysis, multinuclear NMR, and X-ray diffraction crystallography.