Two-Dimensional, Pyrazine-Based Nonlinear Optical Chromophores with Ruthenium(II) Ammine Electron Donors

Six new nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by complexing a known pro-ligand with electron donating {Ru^(II)(NH_3)_5}^(2+) or trans-{Ru^(II)(NH_3)_4(py)}^(2+) (py = pyridine) centers. These cationic complexes have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible d → π* metal-to-ligand charge-transfer (MLCT) absorptions gain intensity on increasing the number of Ru^(II) centers from one to two, but remain at constant energy. One or two Ru^(III/II) redox processes are observed which are reversible, quasi-reversible, or irreversible, while all of the ligand-based reductions are irreversible. Molecular first hyperpolarizabilities β have been determined by using hyper-Rayleigh scattering (HRS) at 1064 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly two-dimensional (2D) in character, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the MLCT bands also allow the indirect determination of estimated static first hyperpolarizabilities β_0. Both the HRS and the Stark-derived β_0 values increase on moving from mono- to bimetallic complexes, and substantial enhancements in NLO response are achieved when compared with one-dimensional (1D) and 2D monometallic Ru^(II) ammine complexes reported previously

Syntheses and Properties of Two-Dimensional, Dicationic Nonlinear Optical Chromophores Based on Pyrazinyl Cores

Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, π → π* intramolecular charge-transfer (ICT) transitions on replacing −OMe with –Nme_2 substituents arise from the stronger π-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities β have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant “off-diagonal” β_(zyy) components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large, and the Stark-derived β_0 response for one of the new salts is several times greater than that determined for (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear RuII ammine complex salts

Quadratic and Cubic Nonlinear Optical Properties of Salts of Diquat-Based Chromophores with Diphenylamino Substituents

A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2′-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense π → π* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by “off-diagonal” β_(zyy) components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E_(1/2) values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based β_0 responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520−1600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores

Syntheses and Properties of Salts of Chromophores with Ferrocenyl Electron Donor Groups and Quaternary Nitrogen Acceptors

A series of five new dipolar cations has been synthesized with ferrocenyl (Fc) electron donor groups connected to N-arylpyridinium, N-methylquinolinium, N-methylbenzothiazolium, or N-methylacridinium acceptors. Together with their known N-methylpyridinium analogue, these chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Nine single-crystal X-ray structures have been determined, including two polymorphs of one salt obtained from a single crystallization experiment, and two of these are polar materials. A highly favorable degree of dipolar alignment for bulk NLO effects is observed in one case. Molecular quadratic nonlinear optical (NLO) responses have been determined by using femtosecond hyper-Rayleigh scattering (HRS) at 1300 nm and also via Stark (electroabsorption) spectroscopic studies on the intense π → π^* intraligand and d → π^* metal-to-ligand charge-transfer bands. A broad correlation between the electron acceptor strength and the HRS-derived first hyperpolarizabilities β and the static first hyperpolarizabilities β0 estimated from the Stark data is evident. This is the first time that meaningful (albeit indirectly determined) β_0 data have been reported for Fc compounds, allowing quantitative comparisons with the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium (DAS) tosylate. The observed β_0 values are in several cases similar to that of [DAS]PF_6, and possibly even larger in one instance

Synthesis, Characterization, and Reactivity of Ethynyl- and Propynyl-Terminated Si(111) Surfaces

Ethynyl- and propynyl-terminated Si(111) surfaces synthesized using a two-step halogenation/alkylation method have been characterized by transmission infrared spectroscopy (TIRS), high-resolution electron energy-loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), atomic-force microscopy (AFM), electrochemical scanning–tunneling microscopy (EC-STM) and measurements of surface recombination velocities (S). For the ethynyl-terminated Si(111) surface, TIRS revealed signals corresponding to ethynyl ≡C–H and C≡C stretching oriented perpendicular to the surface, HREELS revealed a Si–C stretching signal, and XPS data showed the presence of C bound to Si with a fractional monolayer (ML) coverage (Φ) of Φ_(Si–CCH) = 0.63 ± 0.08 ML. The ethynyl-terminated surfaces were also partially terminated by Si–OH groups (Φ_(Si–OH) = 0.35 ± 0.03 ML) with limited formation of Si^(3+) and Si^(4+) oxides. For the propynyl-terminated Si(111) surface, TIRS revealed the presence of a (C–H)CH_3 symmetric bending, or “umbrella,” peak oriented perpendicular to the surface, while HREELS revealed signals corresponding to Si–C and C≡C stretching, and XPS showed C bound to Si with Φ_(Si–CCCH_3) = 1.05 ± 0.06 ML. The LEED patterns were consistent with a (1 × 1) surface unit cell for both surfaces, but room-temperature EC-STM indicated that the surfaces did not exhibit long-range ordering. HCC–Si(111) and CH_3CC–Si(111) surfaces yielded S values of (3.5 ± 0.1) × 10^3 and (5 ± 1) × 10^2 cm s^(–1), respectively, after 581 h exposure to air. These observations are consistent with the covalent binding of ethynyl and propynyl groups, respectively, to the Si(111) surface

Effects of anti-triadin antibody on Ca2+ release from sarcoplasmic reticulum

AbstractThe monoclonal antibody, mAb GE 4.90, raised against triadin, a 95 kDa protein of sarcoplasmic reticulum (SR), inhibits the slow phase of Ca2+ release from SR following depolarization of the T-tubule moiety of the triad. The antibody has virtually no effect on the fast phase of depolarization-induced Ca2+ release nor on caffeine-induced Ca2+ release. Since the slow phase of depolarization-induced Ca2+ release is also inhibited by dihydropyridines (DHP), these results suggest that triadin may be involved in the functional coupling between the DHP receptor and the SR Ca2+ channel

Passivation of Zn_3P_2 substrates by aqueous chemical etching and air oxidation

Surface recombination velocities measured by time-resolved photoluminescence and compositions of Zn_(3)P_2 surfaces measured by x-ray photoelectron spectroscopy (XPS) have been correlated for a series of wet chemical etches of Zn_(3)P_2 substrates. Zn_(3)P_2 substrates that were etched with Br_2 in methanol exhibited surface recombination velocity values of 2.8 × 10^4 cm s^(−1), whereas substrates that were further treated by aqueous HF–H_(2)O_2 exhibited surface recombination velocity values of 1.0 × 10^4 cm s^(−1). Zn_(3)P_2 substrates that were etched with Br_2 in methanol and exposed to air for 1 week exhibited surface recombination velocity values of 1.8 × 10^3 cm s^(−1), as well as improved ideality in metal/insulator/semiconductor devices

Failure modes of protection layers produced by atomic layer deposition of amorphous TiO₂ on GaAs anodes

Amorphous titanium dioxide (a-TiO₂) films formed by atomic layer deposition can serve as protective coatings for semiconducting photoanodes in water-splitting cells using strongly alkaline aqueous electrolytes. Herein, we experimentally examine the mechanisms of failure for p⁺-GaAs anodes coated with a-TiO₂ films (GaAs/a-TiO₂). Galvanic displacement of exposed GaAs by Au allowed imaging of pinholes in the a-TiO₂ coatings, and enabled collection of quantitative and statistical data associated with pinhole defects. A combination of imaging, electrochemical measurements, and quantitative analyses of corrosion products indicated that extrinsic pinholes were present in the a-TiO₂ films before electrochemical operation. During electrochemical operation these pinholes led to pitting corrosion of the underlying GaAs substrate. The dominant source of pinholes was the presence of atmospheric particulate matter on the GaAs surface during deposition of the a-TiO₂ layer. The pinhole density decreased substantially when the thickness of the a-TiO₂ coating increased beyond 45 nm, and approached zero when the thickness of the film exceeded 112 nm. The density of pinholes in films thinner than 45 nm decreased when the a-TiO₂ coating was deposited in an environmentally controlled cleanroom. Pinhole-free GaAs/a-TiO₂ devices were also tested via chronoamperometry to quantify the rate of pinhole formation during electrochemistry. The time-to-failure increased with thickness, suggesting that the failure mechanism may involve diffusion or migration through the film. However, other mechanisms may also contribute to the degradation of thicker films (>112 nm). Nevertheless, as previously hypothesized, extrinsic pinhole defects formed during deposition and testing control the short-term protective performance of the a-TiO₂ film for GaAs anodes evolving O₂ from water

Comparative Study in Acidic and Alkaline Media of the Effects of pH and Crystallinity on the Hydrogen-Evolution Reaction on MoS_2 and MoSe_2

Single crystals of n-type MoS_2 and n-MoSe_2 showed higher electrocatalytic activity for the evolution of H_2(g) in alkaline solutions than in acidic solutions. The overpotentials required to drive hydrogen evolution at −10 mA cm^(–2) of current density for MoS^2 samples were −0.76 ± 0.13 and −1.03 ± 0.21 V when in contact with 1.0 M NaOH(aq) and 1.0 M H_2SO_4(aq), respectively. For MoSe_2 samples, the overpotentials at −10 mA cm^(–2) were −0.652 ± 0.050 and −0.709 ± 0.073 V in contact with 1.0 M KOH(aq) and 1.0 M H_2SO_4(aq), respectively. Single crystals from two additional sources were also tested, and the absolute values of the measured overpotentials were consistently less (by 460 ± 250 mV) in alkaline solutions than in acidic solutions. When electrochemical etching was used to create edge sites on the single crystals, the kinetics improved in acid but changed little in alkaline media. The overpotentials measured for polycrystalline thin films (PTFs) and amorphous forms of MoS_2 showed less sensitivity to pH and edge density than was observed for single crystals and showed enhanced kinetics in acid when compared to alkaline solutions. These results suggest that the active sites for hydrogen evolution on MoS_2 and MoSe_2 are different in alkaline and acidic media. Thus, while edges are known to serve as active sites in acidic media, in alkaline media it is more likely that terraces function in this role

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

New complexes with six ferrocenyl (Fc) groups connected to ZnII or Cd^(II) tris(2,2′-bipyridyl) cores are described. A thorough characterisation of their BPh_(4)− salts includes two single-crystal X-ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(Fe^(II))→π* metal-to-ligand charge-transfer (MLCT) bands accompany the π→π* intraligand charge-transfer absorptions in the near UV region. Each complex shows a single, fully reversible Fe^(III/II) wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper-Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β_0 reaching as high as approximately 10^(−27) esu and generally increasing with π-conjugation extension. Z-scan cubic NLO measurements reveal high two-photon absorption cross-sections σ2 of up to 5400 GM in one case. DFT calculations reproduce the π-conjugation dependence of β_0, and TD-DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature