Configuration-dependent interface charge transfer at a molecule-metal junction

The role of the molecule-metal interface is a key issue in molecular electronics. Interface charge transfer processes for 4-fluorobenzenethiol monolayers with different molecular orientations on Au(111) were studied by resonant photoemission spectroscopy. The electrons excited into the LUMO or LUMO+1 are strongly localized for the molecules standing up on Au(111). In contrast, an ultrafast charge transfer process was observed for the molecules lying down on Au(111). This configuration-dependent ultrafast electron transfer is dominated by an adiabatic mechanism and directly reflects the delocalization of the molecular orbitals for molecules lying down on Au(111). Theoretical calculations confirm that the molecular orbitals indeed experience a localization-delocalization transition resulting from hybridization between the molecular orbitals and metal surface. Such an orientation-dependent transition could be harnessed in molecular devices that switch via charge transfer when the molecular orientation is made to change.     

Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. synthetic, x-ray diffraction, dynamic NMR, EPR, CV, and DFT studies

The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.     

Cobalt-catalyzed hydrogen desorption from the LiNH2-LiBH4 system

A doping of 5 wt% CoCl2 considerably decreases the dehydrogenation temperature of a mixture of LiNH2 and LiBH4. More that 8 wt% of hydrogen can be released at ca. 155 degrees C. X-Ray absorption near edge structure (XANES) spectroscopy indicated the formation of metallic Co after ball milling CoCl2 with LiNH2 and LiBH4. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements revealed that Co particles have poor crystallinity and are finely dispersed in the sample, which could lead to a high catalytic efficiency.     

Synthesis and characterization of a new ternary imide-Li2Ca(NH)2

The ternary imide Li(2)Ca(NH)2 was successfully synthesized by dehydrogenating a mixture of LiNH(2) and CaH(2) at a molar ratio of 2:1 in a stream of purified argon at 300 degrees C. A powder X-ray diffraction measurement revealed that Li(2)Ca(NH)2 was of the trigonal anti-La(2)O(3) structure (space group Pm1) with lattice constants of a = 3.5664(3)A and c = 5.9540(8) A. Ca occupied the 1b site (0, 0, 1/2), Li occupied the 2d site (1/3, 2/3, 0.8841(22)), and N occupied the 2d site (1/3, 2/3, 0.2565(15)). Nuclear magnetic resonance and X-ray absorption fine structure analyses demonstrated that each Li ion was coordinated with four imide ions and each Ca ion was coordinated with six imide ions.     

Charge transfer dynamics of 3,4,9,10-perylene-tetracarboxylic-dianhydride molecules on Au(111) probed by resonant photoemission spectroscopy

Charge transfer dynamics across the lying-down 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) organic semiconductor molecules on Au(111) interface has been investigated using the core-hole clock implementation of resonant photoemission spectroscopy. It is found that the charge transfer time scale at the PTCDA∕Au(111) interface is much larger than the C 1s core-hole lifetime of 6 fs, indicating weak electronic coupling between PTCDA and the gold substrate due to the absence of chemical reaction and∕or bonding.     

Surface transient effects in ultralow‐energy Cs+ sputtering of Si

This study examines the dependence of the sputter rate and the transient width (z_tr) as a function of Cs⁺ primary ion energy (impact energy (E_p) = 320 eV, 500 eV and 1 keV) and incident angles between 0 and 70° . The instrument used was the ATOMIKA 4500 SIMS depth profiler and the sample was Si with ten delta layers of Si_0.7 Ge_0.3. We observed the narrowest transient widths of between 1.4 and 2.0 nm apparent depth. This was achieved at incident angles (θ) of 30–50° . An extended transient effect was observed when profiled at θ > 50° . Below this incident angle, the transient width is less than twice the penetration depth (z_tr < 2R_norm). At minimum z_tr, z_tr ≈ R_norm. The detection sensitivity is best achieved at θ ≈ 30° for all energies investigated. The sputter rate is lowest at normal incidence, rising gradually to a maximum at θ ≈ 50–60° . This is similar to that observed with ultralow‐energy O₂⁺ primary ion beams. 1 At ultralow energies, reducing E_p does not have a significant effect in reducing z_tr. We conclude that for E_p < 1 keV, the optimum condition to achieve minimum z_tr while maintaining good sensitivity and high sputter rate is at θ ≈ 30° . Copyright © 2007 John Wiley & Sons, Ltd.     

Palladium nanoparticles stabilized by an ionic polymer and ionic liquid: a versatile system for C-C cross-coupling reactions

Highly stable palladium nanoparticles (Pd NPs), protected by an imidazolium-based ionic polymer (IP) in a functionalized ionic liquid (IL), have been prepared and characterized by transmission electron microscopy (TEM). These Pd NPs are excellent precatalysts for Suzuki, Heck, and Stille coupling reactions and can be stored without undergoing degradation for at least 2 years. The NP-IP-IL system may therefore be considered as an alternative to the traditional palladium on carbon (Pd/C) precatalyst employed in many C-C coupling reactions, also allowing reactions to be conducted under "solvent-free" conditions.     

Molecular anchor Cu-S formed on a thiophene mediated Si(111)-(7x7) surface

Thiophene molecule selectively binds to the adjacent adatom-rest atom pair on the Si(111)-(7x7) surface through its alpha-carbon atoms, leading to the covalent attachment of a C-S-C linkage and remaining C=C (beta-carbon) bond onto the surface. Photoemission studies show that Cu atom readily adsorbs onto the S atom of the functional group to form the Cu-S molecular anchor in two forms: one points away from the thiophene C=C group; the other points toward the C=C group.     

A supercooled imidazolium iodide ionic liquid as a low-viscosity electrolyte for dye-sensitized solar cells

A series of allyl-functionalized imidazolium salts are reported, including 1-allyl-3-ethylimidazolium iodide and 1-allyl-3-propylimidazolium iodide, which have melting points close to room temperature and show typical properties of supercooled fluids if heated above their melting points. Their viscosities in the liquid state are considerably lower than the benchmark ionic liquid used in solar cells, viz., 1-propyl-3-methylimidazolium iodide. Electrolytes containing these new liquids provide excellent efficiencies and good stability in dye-sensitized solar cells when subjected to an accelerated-light soaking test at 60 degrees C. The structures of three of the new salts have been established in the solid state by single-crystal X-ray analysis.     

Ultrafast electron transfer from oligo(p-phenylene-ethynylene)thiol to gold

The electron transfer dynamics of oligo(p-phenylene-ethynylene) (OPE) SAM on Au(111) was studied by resonant photoemission spectroscopy. The ultrafast electron transfer from OPE molecules to Au substrate was clearly observed. The time scale for this charge transfer is much less than 6 fs, the core-hole lifetime for C 1s. This strongly suggests that there is an intense interfacial electronic coupling between OPE molecules and the Au substrate.