Resistive switching characteristics by using the Al₂O₃ interfacial layer in an Al/Cu/GdO_x/Al₂O₃/TiN memristor have been enhanced as compared to the Al/Cu/GdO_x/TiN structure owing to the insertion of Al₂O₃ layer for the first time. Polycrystalline grain, chemical composition, and surface roughness of defective GdO_x film have been investigated by transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and atomic force microscopy (AFM). For bipolar resistive switching (BRS) characteristics, the conduction mechanism of high resistance state (HRS) is a space-charge limited current for the Al/Cu/GdO_x/TiN device while the Al/Cu/GdO_x/Al₂O₃/TiN device shows Schottky emission. However, both devices show Ohmic at a low resistance state (LRS). After the device has been SET, the Cu filament evidences by both TEM and elemental mapping. Oxygen-rich at the Cu/GdO_x interface and Al₂O₃ layer are confirmed by energy dispersive X-ray spectroscopy (EDS) line profile. The Al/Cu/GdO_x/Al₂O₃/TiN memristor has lower RESET current, higher speed operation of 100 ns, long read pulse endurance of >10⁹ cycles, good data retention, and the memristor with a large resistance ratio of >10⁵ is operated at a low current of 1.5 µA. The complementary resistive switching (CRS) characteristics of the Al/Cu/GdO_x/Al₂O₃/TiN memristor show also a low current operation as compared to the Al/Cu/GdO_x/TiN device (300 µA vs. 3.1 mA). The transport mechanism is the Cu ion migration and it shows Ohmic at low field and hopping at high field regions. A larger hopping distance of 1.82 nm at the Cu/GdO_x interface is obtained as compared to a hopping distance of 1.14 nm in the Al₂O₃ layer owing to a larger Cu filament length at the Cu/GdO_x interface than the Al₂O₃ layer. Similarly, the CRS mechanism is explained by using the schematic model. The CRS characteristics show a stable state with long endurance of >1000 cycles at a pulse width of 1 µs owing to the insertion of Al₂O₃ interfacial layer in the Al/Cu/GdO_x/Al₂O₃/TiN structure.

Phospha-Michael addition, which is the addition reaction of a phosphorus-based nucleophile to an acceptor-substituted unsaturated bond, certainly represents one of the most versatile and powerful tools for the formation of P-C bonds, since many different electrophiles and P nucleophiles can be combined with each other. This offers the possibility to access many diversely functionalized products. In this work, two kinds of basic pyridine-based organo-catalysts were used to efficiently catalyze phospha-Michael addition reactions, the 4-N,N-dimethylaminopyridinium saccharinate (DMAP·Hsac) salt and a fluorous long-chained pyridine (4-R_f-CH₂OCH₂-py, where R_f = C₁₁F₂₃). These catalysts have been synthesized and characterized by Lu’s group. The phospha-Michael addition of diisopropyl, dimethyl or triethyl phosphites to α, β-unsaturated malonates in the presence of those catalysts showed very good reactivity with high yield at 80–100 °C in 1–4.5 h with high catalytic recovery and reusability. With regard to significant catalytic recovery, sometimes more than eight cycles were observed for DMAP·Hsac adduct by using non-polar solvents (e.g., ether) to precipitate out the catalyst. In the case of the fluorous long-chained pyridine, the thermomorphic method was used to efficiently recover the catalyst for eight cycles in all the reactions. Thus, the easy separation of the catalysts from the products revealed the outstanding efficacy of our systems. To our knowledge, these are good examples of the application of recoverable organo-catalysts to the DMAP·Hsac adduct by using non-polar solvent and a fluorous long-chained pyridine under the thermomorphic mode in phospha-Michael addition reactions.

The reaction of [PdCl₂(CH₃CN)₂] and bis-4,4′-(R_fCH₂OCH₂)-2,2′-bpy (1a–d), where R_f = n-C₁₁F₂₃ (a), n-C₁₀F₂₁ (b), n-C₉F₁₉ (c) and n-C₈F₁₇ (d), respectively, in the presence of dichloromethane (CH₂Cl₂) resulted in the synthesis of Pd complex, [PdCl₂[4,4′-bis-(R_fCH₂OCH₂)-2,2′-bpy] (2a–d). The Pd-catalyzed Stille arylations of vinyl tributyltin with aryl halides were selected to demonstrate the feasibility of recycling usage with 2a as the catalyst using NMP (N-methyl-2-pyrrolidone) as the solvent at 120–150 °C. Additionally, recycling and electronic effect studies of 2a–c were also carried out for Suzuki-Miyaura reaction of phenylboronic acid derivatives, 4-X-C₆H₄-B(OH)₂, (X = H or Ph) with aryl halide, 4-Y-C₆H₄-Z, (Y = CN, H or OCH₃; Z = I or Br) in dimethylformamide (DMF) at 135–150 °C. At the end of each cycle, the product mixtures were cooled to lower temperature (e.g., −10 °C), and then catalysts were recovered by decantation with Pd leaching less than 1%. The products were quantified by gas chromatography/mass spectrometry (GC/MS) analysis or by the isolated yield. The complex 2a-catalyzed Stille reaction of aryl iodides with vinyl tributyltin have good recycling results for a total of 8 times, with a high yield within short period of time (1–3 h). Similarly, 2a–c-catalyzed Suzuki-Miyaura reactions also have good recycling results. The electronic effect studies from substituents in both Stille and Suzuki-Miyaura coupling reactions showed that electron withdrawing groups speed up the reaction rate. To our knowledge, this is the first example of recoverable fluorous long-chained Pd-catalyzed Stille reactions under the thermomorphic mode.

Homogeneous catalysts PtCl₂[5,5′-bis-(n-ClCF₂(CF₂)₃CH₂OCH₂)-2,2′-bpy] (2A) and PtCl₂[5,5′-bis-(n-HCF₂(CF₂)₃CH₂OCH₂)-2,2′-bpy] (2B), which contained short fluorous chains, were synthesized and used in catalysis of hydrosilylation of alkynes. In these reactions the thermomorphic mode was effectively used to recover these catalysts from the reaction mixture up to eight cycles by taking advantage of heterogeneous phase separation at ice temperature. This kind of catalysis had previously been observed in fluorous catalysts of platinum containing about 50% F-content, but in this work the percentage of F-content is decreased to only about 30%, by which we termed them as “very light fluorous”. Our new type of catalyst with limited number of F-content is considered as the important discovery in the fluorous technology field as the reduced number of fluorine atoms will help to be able to comply the EPA 8-carbon rule. The metal leaching after the reaction has been examined by ICP-MS, and the testing results show the leaching of residual metal to be minimal. Additionally, comparing these results to our previous work, fluorous chain assisted selectivity has been observed when different fluorous chain lengths of the catalysts are used. It has been found that there exists fluorous chain assisted better selectivity towards β-(E) form in the Pt-catalyzed hydrosilylation of non-symmetric terminal alkyne when the Pt catalyst contains short fluorous chain (i.e., 4 Cs). Phenyl acetylenes showed the opposite regioselectivity due to pi-pi interaction while using the same catalyst via Markovnikov’s addition to form terminal vinyl silane, which is then a major product for Pt-catalyzed hydrosilylation of terminal aryl acetylene with triethylsilane. Finally, the kinetic studies indicate that the insertion of alkyne into the Pt-H bond is the rate-determining step.