Synthesis of β-Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)₂ · H₂O] ( 5 ) produced [Cu(1-(2-cC₅H₆(O))C(Me)NCH₂)₂)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)^[1] gave [Cu(μ-OAc)( L )(H₂O)]₂ ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu₂O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N₂, 60 mL · min^–1; O₂, 60 mL · min^–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L^–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min^–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O₂) with up to 13 mol-% C impurity.     

RuII and RuIII Chloronitrile Complexes: Synthesis,Reaction Chemistry,Solid State Structure,and (Spectro)Electrochemical Behavior

The synthesis of [Ti₆O₄(OiPr)₈(O₂CPh)₈] ( 3 ) and [RuCl(N≡CR)₅][RuCl₄(N≡CR)₂] ( 4a , R = Me; 4b , R = Ph), [Ru(N≡CPh)₆][RuCl₄(N≡CPh)₂] ( 5 ) and [H₃O][RuCl₄(N≡CMe)₂] ( 7a ) is discussed. Crystallization of 5 from CH₂Cl₂ gave trans-[RuCl₂(N≡CPh)₄] ( 6 ). The solid-state structures of 3 , 4a , b , 5 , 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π-interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a , b and 6 was studied at 25 and –72 °C and the results thereof are compared with [NEt₄][RuCl₄(N≡CMe)₂] ( 7b ) and [RuCl(N≡CPh)₅][PF₆] ( 8 ). The electrochemical response of the cation and the anion in 4a , b are independent from each other. [RuCl(N≡CR)₅]⁺ possesses one reversible Ru^II/Ru^III process. However, [RuCl₄(N≡CMe)₂]^– was shown to be prone to ligand exchange and disproportionation upon formation of either a Ru^IV and Ru^II species at 25 °C, while at –72 °C the rapid conversion of the electrochemically formed species is hindered. In situ IR and UV/Vis/NIR studies confirmed the respective disproportionation reaction products of the aforementioned oxidation and reduction, respectively.     

原子力／摩擦力显微图象的分析与测量

用表面粗糙度评定方法和分形几何方法，结合原子力／摩擦力显微图象的特点，编制了包括Ｒａ，Ｒｑ，Ｓｍ，Ｓ，λａ，λｑ及高度分布、承载率曲线、相关函数、功率谱和分形维数等参数的图象分析与测量的ＦＯＲＴＲＡＮ程序；用ＳＴＲ－１８０和ＳＴＲ－１０００标样作了高度标定，对国产Ｎａｔｕｒｅ磁带和进口Ｓｏｎｙ磁带的原子力／摩擦力显微图象进行了分析测量．结果表明：Ｎａｔｕｒｅ磁带的粗糙度和粒度均比Ｓｏｎｙ磁带的大；微摩擦力与表面轮廓及表面轮廓斜率之间均有良好的对应关系．     

Nonideal double-slope effect in organic field-effect transistors

With the development of device engineering and molecular design,organic field effect transistors(OFETs)with high mobility over 10 cm2 V-1-s-1 have been reported.However,the nonideal doubleslope effect has been frequently observed in some of these OFETs,which makes it difficult to extract the intrinsic mobility OFETs accurately,impeding the further application of them.In this review,the origin of the nonideal double-slope effect has been discussed thoroughly,with affecting factors such as contact resistance,charge trapping,disorder effects and coulombic interactions considered.According to these discussions and the understanding of the mechanism behind double-slope effect,several strategies have been proposed to realize ideal OFETs,such as doping,molecular engineering,charge trapping reduction,and contact engineering.After that,some novel devices based on the nonideal double-slope behaviors have been also introduced.     

SPE–HPLC–MS/MS method for the trace analysis of tobacco‐specific N‐nitrosamines and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol in rabbit plasma using tetraazacalix[2]arene[2]triazine‐modified silica as a sorbent

Tobacco‐specific N‐nitrosamines (TSNAs), including N′‐nitrosonornicotine, 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, N′‐nitrosoanatabine, and N′‐nitrosoanabasine, have been implicated as a source of carcinogenicity in tobacco and cigarette smoke. We present a rapid and effective method comprising SPE based on tetraazacalix[2]arene[2]triazine‐modified silica as sorbent and analysis with HPLC–MS/MS for the determination of TSNAs and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a metabolite of 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, in rabbit plasma. The linear dynamic ranges were 10–2000 pg/mL for NNAL and 4–2000 pg/mL for the four TSNAs with good correlation coefficients (>0.9965). The LODs were in the range of 0.9–3.7 pg/mL, and the LOQs were between 2.9 and 12.3 pg/mL. The accuracies of the method were also evaluated and found to be in the range of 90.1–113.3%. This method is promising to be applied to the preconcentration and determination of TSNAs and NNAL in smoke and human body fluids.     

Controlling the orientation and coverage of silica-MFI zeolite films by surface modification

The silica-MFI (Si-MFI) zeolite films are fabricated on α-Al₂O₃ supported silica-zirconia layers. The roughness and chemistry of the substrate surface are changed by surface modification with hydrogen peroxide and carboxymethyl chitosan (CMCS) solution to investigate their effects on the formation and orientation control of Si-MFI zeolite films. The AFM images reveal that the roughness of the silica-zirconia surface can be increased under the treatment of hydrogen peroxide. The Si-MFI zeolite films grown on the rough substrate surface are also b-oriented. Diffuse-reflectance FT-IR studies demonstrate that the abundance of functional groups such as -OH and -COOH can be successfully seeded onto the α-Al₂O₃ supported silica-zirconia layer through modification with CMCS solution. Continuous b-oriented Si-MFI zeolite films can be fabricated on the CMCS-modified α-Al₂O₃ supported silica-zirconia layer. It is evident that the orientation and microstructure of Si-MFI zeolite films on α-Al₂O₃ supported silica-zirconia layers are dominantly controlled by the chemical nature of the substrate surface, where the functional groups serve as the structure-directing matrix to induce the orientation and growth of the zeolite crystals with their b-axes perpendicular to the substrate surface.