Decarboxylative cyanation and thiocyanation via catalytic electron donor-acceptor complex with copper catalysis

A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.

Investigation on ab initio calculations of the electron donor-acceptor complex H_3N·SiH_3Cl and the hypervalence of Si in it

The formation and the presence of hypervalent Si in the electron donor-acceptor com- plex H_3N·SiH_3 Cl have been investigated by ab initio calculation. The results show that there is a 0.707eV decrease of energy when the complex H_3N.SiH_3 Cl is formed from NH_3 and H_3SiCl, the interaction potential between the donor NH_3 and the acceptor H_3SiCl belongs to the Morse type, and the bond angle A(H-Si-Cl) versus bond length d(N-Si) presents a linear relation. The results also show that the interaction is mainly from giving the lone pair electrons in HOMO of NH_3 to LUMO of H_3SiCl, in which the 2P_z of N and the 3d_0 of Si play important role. Bond N-Si is a weak n-σ*type dative one.

Effects of Membrane Lipids on the Electron Transfer Activity of Cytochrome b_6f Complex from Spinach

A lipid_depleted cytochrome b 6f (Cyt b 6f) preparation was obtained from spinach (Spinacia oleracea L.) chloroplasts. Upon reconstitution of this preparation with the membrane lipids purified from spinach thylakoid, the effects of different membrane lipids on the electron transfer activity were studied. The results show that the electron transfer activity of Cyt b 6f is obviously stimulated to different extents, respectively, by monogalactosyldiacylglycerol (MGDG), digalactosyldiacylglycerol (DGDG), phosphatidylcholine (PC), phosphatidylglycerol (PG) and sulfoquinovosyldiacylglycerol (SQDG), and that the extents of stimulation may be closely related to the charge of the membrane lipids. The stimulation of non_charged lipids (MGDG, DGDG) and neutrally_charged lipid (PC) was high with a maximum enhancement of 89%, 75% and 77%, respectively; but the stimulation of two kinds of negatively_charged lipid (PG and SQDG) was relatively low with a maximum enhancement of 43% and 26%, respectively.

Programmable robotized‘transfer-and-jet’printing for large,3D curved electronics on complex surfaces

Large,3D curved electronics are a trend of the microelectronic industry due to their unique ability to conformally coexist with complex surfaces while retaining the electronic functions of 2D planar integrated circuit technologies.However,these curved electronics present great challenges to the fabrication processes.Here,we propose a reconfigurable,mask-free,conformal fabrication strategy with a robot-like system,called robotized‘transfer-and-jet’printing,to assemble diverse electronic devices on complex surfaces.This novel method is a ground-breaking advance with the unique capability to integrate rigid chips,flexible electronics,and conformal circuits on complex surfaces.Critically,each process,including transfer printing,inkjet printing,and plasma treating,are mask-free,digitalized,and programmable.The robotization techniques,including measurement,surface reconstruction and localization,and path programming,break through the fundamental constraints of 2D planar microfabrication in the context of geometric shape and size.The transfer printing begins with the laser lift-off of rigid chips or flexible electronics from donor substrates,which are then transferred onto a curved surface via a dexterous robotic palm.Then the robotic electrohydrodynamic printing directly writes submicrometer structures on the curved surface.Their permutation and combination allow versatile conformal microfabrication.Finally,robotized hybrid printing is utilized to successfully fabricate a conformal heater and antenna on a spherical surface and a flexible smart sensing skin on a winged model,where the curved circuit,flexible capacitive and piezoelectric sensor arrays,and rigid digital–analog conversion chips are assembled.Robotized hybrid printing is an innovative printing technology,enabling additive,noncontact and digital microfabrication for 3D curved electronics.

Control of the Electronic Structure of Manganese Nitrido Complexes by Para Ring Substituents：a Theoretical Study

The relationship between the electronic structures of manganese nitrido complexes and the substituted ligands is investigated by using density functional theory.By designing a series of manganese nitrido complexes [Mn（SalenR）N]＋ with different para ring substituents（R = H,CH_3,NH_2,OCH_3,NMeF,etc） of the ancillary ligand,the properties of manganese-nitrogen bonds were compared for two kinds of electronic structures,of which the radical resides on metal center or the coordinated ring ligand.Our calculation shows that for R = H,CH_3 and NH_2,the [Mn（SalenR）N]＋ complexes have a high-valent Mn（VI） center,and for R = OCH_3 and NMeF,the complexes represent a configuration where the radical delocalizes on the ligand.It is found that the relative energies of these two species depend on electronic properties of the substituent,originating from the intrinsic property of HOMO-LUMO gaps.

Molecular Design and Electronic Structure of Polynuclear Rare Earth Complexes and Clusters

Studies on the electronic structure,molecular design,syntheses of some novel series of tetranuclear rare earth complexes in our laboratory have been reviewed.Spin-unrestricted localized INDO method was used to calculate the electronic structure and the chemical bonding in the typical rare earth cluster Sc[Sc_6Cl_(12)Co]was discussed.

Infrared studies of oxygen-related complexes in electron-irradiated Cz-Si

This paper investigates the infrared absorption spectra of oxygen-related complexes in silicon crystals irradiated with electron （1.5 MeV） at 360 K.Two groups of samples with low [Oi] = 6.9 x 10^17 cm^-3 and high [Oi] = 1.06 x 10^18 cm^-3 were used.We found that the concentration of the VO pairs have different behaviour to the annealing temperature in different concentration of oxygen specimen,it is hardly changed in the higher concentration of oxygen specimen.It was also found that the concentration of VO2 in lower concentration of oxygen specimen gets to maximum at 450 ℃ and then dissapears at 500 ℃,accompanied with the appearing of VO3. For both kinds of specimens,the concentration of VO3 reachs to maximum at 550 ℃ and does not disappear completely at 600 ℃.

Electronic Structure and Chemical Bonding of a Tetranuclear Neodymium Complex Nd_4O(OR)_4(NR'_2)_6

The nonrelativistic DV-X_α-SCC method was used to study the electronic structure and chemi- cal bonding of tetranuclear neodymium complex Nd_4O(OR)_4(NR′_2)_6,with emphasis on the bonding charac- ter of the central μ_4-O atom and the four Nd atoms.The results of calculation show that the μ_4-O atom uses its sp^3 valence orbitals to contribute four O-Nd bonding MOs with character of multicenter bond apparent- ly.The Mulliken population analysis shows that the overlap population between Nd atoms is almost equal to zero,therefore there is no direct metal-metal bond between Nd atoms.The coordination number of Nd in the complex is discussed briefly.

Electronic structure & yield strength prediction for dislocation-Mo complex in the γ phase of nickel-based superalloys

Molybenum＇s effects when added in the γ phase of nickel-based superalloys were studied using the lattice Green＇s function multiscale method. The electronic structure of the dislocation-Mo complex was analyzed and hybridization was found to contribute to the strengthening. Moreover, by combining the interaction energies calculated from two scales, the yield stress was theoretically predicted at 0 K and finite temperature.

Ab Initio Molecular Orbital Calculation on Dinuclear Gold(Ⅰ) Complexes──Metal-Metal Interaction and Electronic Structure of Binuclear Gold(Ⅰ) Complexes with Bridging Bidentate Ligands

The electronic structure and electronic absorption spectra of binuclear Au(Ⅰ) complexes with bidentate phophines and a bidentate ylid ligand have been studied using quasirelativistic pseudopotential ab initio calculations at the HF and MP2 levels by the LANL2DZ basis sets. The electronic properties of the spectral transition and Au(Ⅰ)—Au(Ⅰ) interaction were also discussed.

The Electronic Structures and Chemical Bonding of Some Dinuclear and Trinuclear Low-valence Molybdenum Complexes Containing Thiolate Bridges

The electronic structures of several dinuclears and trinuclears of molybdenum containing thiolates complexes have been calculated by quantum chemistry SCC-DV-Xa method, and the reactivity of complexes has been analyzed in terms of the molecular orbital energy level diagrams, orbital characters and charge populations.

Nonlinear Dynamics in a Nonextensive Complex Plasma with Viscous Electron Fluids

Cylindrical and spherical dust-electron-acoustic （DEA） shock waves and double layers in an unmagnetized, col- lisionless, complex or dusty plasma system are carried out. The plasma system is assumed to be composed of inertial and viscous cold electron fluids, nonextensive distributed hot electrons, Maxwellian ions, and negatively charged stationary dust grains. The standard reductive perturbation technique is used to derive the nonlinear dynamical equations, that is, the nonplanar Burgers equation and the nonplanar further Burgers equation. They are also numerically analyzed to investigate the basic features of shock waves and double layers （DLs）. It is observed that the roles of the viscous cold electron fluids, nonextensivity of hot electrons, and other plasma parameters in this investigation have significantly modified the basic features （such as, polarity, amplitude and width） of the nonplanar DEA shock waves and DLs. It is also observed that the strength of the shock is maximal for the spherical geometry, intermediate for cylindrical geometry, while it is minimal for the planar geometry. The findings of our results obtained from this theoretical investigation may be useful in understanding the nonlinear phenomena associated with the nonplanar DEA waves in both space and laboratory plasmas.

Study on Electronic Structure of Rare Earth Complex with Dioxygen

The electronic structure and chemical bonding of[Ce(CO_3)_3O_2]_2^(8-) have been studied by INDO (Intermediate Neglect of Differentiated Overlap)method in this paper.The results obtained show that the HOMO of[Ce(CO_3)_3O_2]_2^(8-) is mainly composed of the anti-bonding π orbitals of the pcroxide ion(O_2^(2-)) and the LUMO is mainly composed of the 4f orbitals of the Ce(Ⅳ).The peroxide ion coordinates to ceric ion by means of σ and π dative bonds.After coordination the O-O bond of the peroxide ions is strengthened.By comparison with cerous complexes,the contribution of the 4f orbitals to bonding increases in the ceric com- plex.

Imaging Ultrafast Plasmon Dynamics within a Complex Dolmen Nanostructure Using Photoemission Electron Microscopy

We report direct nanoscale imaging of ultrafast plasmon in a gold dolmen nanostructure excited with the 7is laser pulses by combining the interferometric time-resolved technology with the three-photon photoemission electron microscopy （PEEM）. The interferometric time-resolved traces show that the plasmon mode beating pattern appears at the ends of the dimer slabs in the dolmen nanostructure as a result of coherent superposition of multiple localized surface plasmon modes induced by broad bandwidth of the ultrafast laser pulses. The PEEM measurement further discloses that in-phase of the oscillation field of two neighbor defects are surprisingly observed, which is attributed to the plasmon coupling between them. Furthermore, the control of the temporal delay between the pump and probe laser pluses could be utilized for manipulation of the near-field distribution. These findings deepen our understanding of ultrafast plasmon dynamics in a complex nanosystem.

SYNTHESIS AND ELECTRONIC SPECTRA OF RUTNENIUM(Ⅱ)-1,1'-BIISOQUINOLINE COMPLEXES

l,l'-biisoquinoline can coordinate with ruthenfum(Ⅱ) to form a new series of mononuclear complexes and the electronic absorption of these complexes were measured and reasonably assigned.

Aqueous Sn-S Complex Derived Electron Selective Layer for Perovskite Solar Cells

A novel aqueous Sn-S complex solution was applied as precursor to fabricate SnO2 electron selective layers (ESLs) for the hybrid perovskite solar cells (PSCs).The tin and sulfur powder were directly dissolved in a (NH4)2S water solution to form Sn-S precursor.After depositon and annealing,the SnO2 film was formed,presenting as a low cost and enviromental friendly method for preparation of ESL.The films showed excellent transmittance at visible wavelength range.Moreover,the method exhibited high compatibility for doping using Cu,Cd,Li,and Zn elements.Zn doping (0.05 M) in the as-prepared SnO2 ESL significantly improved perovskite solar cells (PSCs) performance.The highest PCE of 13.17% was achived with 15% enhancement compared to that of undoped SnO2 ESL samples.TiCl4 modifications on SnO2 film improved photovoltaic performance to 14.45%,but resulted in the poor long-term stability,around 80% more degredation than that of PSCs based on Zn-doped SnO2 films.

Effect of Boron (Nitrogen)-Divacancy Complex Defects on the Electronic Properties of Graphene Nanoribbon

We report the effect of boron (nitrogen)-divacancy complex defects on the electronic properties of graphene nanoribbon by means of density functional theory. It is found that the defective subbands appear in the conduction band and valence band in accordance with boron (nitrogen)-divacancy defect, respectively;the impurity subbands don’t lead to the transition from the metallic characteristic to a semiconducting one. These complex defects affect the electronic band structures around the Fermi level of the graphene nanoribbon;the charge densities of these configurations have also changed distinctly. It is hoped that the theoretical results are helpful in designing the electronic device.

Ion Nonthermality Induced Nonlinear Dust Acoustic Wave Propagation in a Complex Plasma in Presence of Weak Secondary Electron Emission from Dust Grains

In this paper we have investigated the effect of ion nonthermality on nonlinear dust acoustic wave propagation in a complex plasma in presence of weak secondary electron emission from dust grains. Equilibrium dust charge in this case is negative. Dusty plasma under our consideration consists of inertialess nonthermal ions, Boltzman distributed primary and secondary electrons and negatively charged inertial dust grains. Both adiabatic and nonadiabatic dust charge variations have been taken into account. Our analysis shows that in case of adiabatic dust charge variation, at a fixed non-zero ion nonthermality increasing secondary electron emission decreases amplitude and increases width of the rarefied dust acoustic soliton whereas for a fixed secondary electron yield increasing ion nonthermality increases amplitude and decreases width of such rarefied dust acoustic soliton. Thus shape of the soliton may be retained if strength of both the secondary electron yield and the ion nonthermality are increased. Nonadiabatic dust charge variation shows that, at fixed non-zero ion nonthermality, increasing secondary electron emission suppresses oscillation of oscillatory dust acoustic shock at weak nonadiabaticity and pronounces monotonicity of monotonic dust acoustic shock at strong nonadiabaticity. On the other hand at a fixed value of the secondary electron yield, increasing ion nonthermality enhances oscillation of oscillatory dust acoustic shock at weak nonadiabaticity and reduces monotonicity of monotonic dust acoustic shock at strong nonadiabaticity. Thus nature of dust acoustic shock may also remain unchanged if both secondary electron yield and ion nonthermality are increased.

ELECTRONIC STRUCTURE AND BOND CHARACTER OF COMPLEXES OF RARE EARTH CHLORIDES WITH CROWN ETHERS

A series of lanthanide complexes LnCl_3·L(Ln=La,Pr,Nd;L=15-C-5 or 18-C-6)have been synthesized and their molecular configuration,electronic structure and bond character have been studied by XPS and quantum chemical calculation.The calculated results are in good agreement with that obtained in the experiments.Three Cl atoms are on the same side of Ln in LnCl_3·15-C-5 and the crown ring on the other side.forming a complex molecule with coordination number 8.LnCl_3·15-C-5 is easily hygroscopic in air because of its unsaturated coordination,which differs sharply from the stable Ln(NO_3)_3·15-C-5 com- plex of coordination number 11.The HOMO and neighboring occupied MOs are composed of Cl 3p and O2p, and the LUMO and neighboring unoccupied MOs are composed of Ln orbitals.The level structure easily pro- duces Ln3d satellite in XPS caused by L→Ln charge transfer transition.Due to the coordination,the absolute values of the charge are decreased at Ln and O atoms,but increased at Cl atoms,which is in agreement with XPS results.